| PATENT ASSIGNEE'S COUNTRY | Germany |
| UPDATE | 09.99 |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 14.09.99 |
| PATENT TITLE |
Polymeric polyamines from alternating polyketones |
| PATENT ABSTRACT |
Polymeric polyamines obtainable by reacting linear, alternating carbon monoxide/1-alkene copolymers with ammonia or amines of the formula (I) R--NH.sub.2 (I) where R is --NH.sub.2, --OH, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.20 -aryl, C.sub.7 -C.sub.20 -arylalkyl, C.sub.7 -C.sub.20 -alkylaryl or an organosilicon radical having 3 to 30 carbon atoms, or with a reagent which releases ammonia or the amine (I), and subsequent hydrogenation. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | 17.12.97 |
| PATENT FOREIGN APPLICATION PRIORITY DATA | This data is not available for free |
| PATENT REFERENCES CITED | This data is not available for free |
| PATENT CLAIMS |
We claim: 1. A polymeric polyamine comprising less than 5% by weight of carbonyl groups, based on the polymeric polyamine, obtained by reacting linear, alternating carbon monoxide/1-alkene copolymers with ammonia or amines of the formula (I) R--NH.sub.2 (I) where R is --NH.sub.2, --OH, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.20 -aryl, C.sub.7 -C.sub.20 -arylalkyl, C.sub.7 -C.sub.20 -alkylaryl or an organsilicon radical having 3 to 30 carbon atoms, or with a reagent which releases ammonia or the amine (I), and subsequently hydrogenating the reacted copolymers. 2. A polymeric polyamine as claimed in claim 1, wherein the 1-alkene is ethylene. 3. A polymeric polyamine as claimed in claim 1, wherein the content of chemically bonded oxygen in the polymeric polyamine is in the range from 0 to 10% by weight. 4. A polymeric polyamine as claimed in claim 1, which has a number average molecular weight Mn in the range from 100 to 1,000,000. 5. A process for preparing a polymeric polyamine which comprises less than 5% by weight of carbonyl groups, based on the polymeric polyamine, which process comprises reacting linear, alternating carbon monoxide/1-alkene copolymers with ammonia or amines of the formula (I) R--NH.sub.2 (I) where R is --NH.sub.2, --OH, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.20 -aryl, C.sub.7 -C.sub.20 -arylalkyl, C.sub.7 -C.sub.20 -alkylaryl or an organsilicon radical having 3 to 30 carbon atoms, or with a reagent which releases ammonia or the amine (I), and subsequently hydrogenating the reacted copolymers. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
The present invention relates to polymeric polyamines obtainable by reacting linear, alternating carbon monoxide/1-alkene copolymers with ammonia or amines of the formula (I) R--NH.sub.2 (I) where R is --NH.sub.2, --OH, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.20 -aryl, C.sub.7 -C.sub.20 -arylalkyl, C.sub.7 -C.sub.20 -alkylaryl or an organosilicon radical having 3 to 30 carbon atoms, or with a reagent which releases ammonia or the amine (I), and subsequent hydrogenation, to a process for preparing polymeric polyamines by reacting carbon monoxide/1-alkene copolymers with ammonia or amines of the formula (I) R--NH.sub.2 (I) where R is --NH.sub.2, --OH, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.20 -aryl, C.sub.7 -C.sub.20 -arylalkyl, C.sub.7 -C.sub.20 -alkylaryl or an organosilicon radical having 3 to 30 carbon atoms, or with a reagent which releases ammonia or the amine (I), and subsequent hydrogenation, and to the use of the polymeric polyamines as surfactants, dispersant, paper auxiliary, soil remover, component in skin creams and hair care, crosslinker for adhesives, stabilizer for polyoxymethylene, corrosion inhibitors, textile assistant, auxiliary for dispersions, adhesives, protective colloids, adhesive coating, epoxy hardener in aqueous dispersions, auxiliary for dishwashing compositions, leveling agent for textiles, solubilizer for cosmetics, auxiliary for metal extraction, complexing agent, fuel additive, lubricants, corrosion inhibitor for aqueous systems, addition to size and resin raw materials, auxiliary for dye fixation on textiles, auxiliary in paper fixing, retention aid, complexing agent for metal recycling, stabilizers for hydroxylamine, or color transfer inhibitors. Polymeric polyamines are important auxiliaries for example in the paper or detergent industry. They are generally obtained by polymerizing nitrogen-containing monomers. The properties of the currently available polymeric polyamines are, as a rule, determined by the structure and reactivity of the monomers and must be adapted to diverse purposes of use. The small number of commercially available nitrogen monomers means that this adaptation is possible only with limitations. The properties of the polymer are normally determined not only by the N/C ratio but also by the nature of the N functionality. Thus, it is desirable to influence the molar ratio of primary, secondary or tertiary N functionalities. It is an object of the present invention to provide polymeric polyamines with varying properties and a relatively large proportion of amine groups, if possible by means of a variable process. We have found that this object is achieved by the polymeric polyamines obtainable by reacting linear, alternating carbon monoxide/1-alkene copolymers with ammonia or amines of the formula (I) R--NH.sub.2 (I) where R is --NH.sub.2, --OH, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.20 -aryl, C.sub.7 -C.sub.20 -arylalkyl, C.sub.7 -C.sub.20 -alkylaryl or an organosilicon radical having 3 to 30 carbon atoms, or with a reagent which releases ammonia or the amine (I), and subsequent hydrogenation, and by a process for preparing polymeric polyamines by reacting carbon monoxide/1-alkene copolymers with ammonia or amines of the formula (I) R--NH.sub.2 (I) where R is --NH.sub.2, --OH, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.20 -aryl, C.sub.7 -C.sub.20 -arylalkyl, C.sub.7 -C.sub.20 -alkylaryl or an organosilicon radical having 3 to 30 carbon atoms, or with a reagent which releases ammonia or the amine (I), and subsequent hydrogenation, using linear alternating carbon monoxide/1-alkene copolymers. We have furthermore found the use of the polymeric polyamines defined at the outset inter alia as surfactants and dolor transfer inhibitors. Linear, alternating carbon monoxide/1-alkene copolymers (alternating polyketones) underlying the polymeric polyamines are known and can generally be obtained by palladium-catalyzed copolymerization of carbon monoxide with a 1-alkene or a plurality of 1-alkenes. As a rule they have the following repeating unit. ##STR1## In this, X is hydrogen, C.sub.1 -C.sub.10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, n-octyl or n-decyl, but preferably hydrogen or methyl. The linear alternating copolymers thus also include polymers with more than one type of structural units derived from 1-alkene, such as carbon monoxide/ethylene/propene terpolymers. The carbonyl group:alkylene structural unit molar ratio in the alternating polyketones is normally 1:1. The average molecular weight Mn of the linear, alternating carbon monoxide/1-alkene copolymers, determined by the NMR spectroscopic method, is normally in the range from 100 to 1,000,000, preferably in the range from 150 to 500,000, in particular in the range from 100 to 50,000. The novel polymeric polyamines can be obtained by reacting the described linear, alternating carbon monoxide/1-alkene copolymers with ammonia, amines of the formula R--NH.sub.2 (I) or with a reagent which releases ammonia or the amines (I), and subsequent hydrogenation. Suitable R radicals in (I) are --NH.sub.2, --OH, C.sub.1 -C.sub.10 -alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, n-decyl, and furthermore C.sub.6 -C.sub.20 -aryl such as phenyl, naphthyl, C.sub.7 -C.sub.20 -arylalkyl such as benzyl and C.sub.7 -C.sub.20 alkylaryl such as p-tolyl, o-tolyl, xylyl. Further suitable R radicals in (I) are organosilicon radicals having 3 to 30 carbon atoms, thus tri(C.sub.1 -C.sub.10 alkyl)silyl such as trimethylsilyl, tert-butyldimethylsilyl or else triarylsilyl, for example triphenylsilyl, tri-p-tolylsilyl or trinaphthylsilyl. Generally suitable reagents releasing ammonia are all ammonium salts, preferably ammonium carbonate, ammonium acetate and ammonium formate. Preferably used as aminating reagent is ammonia, hydrazine or ammonium carbonate, where appropriate in the form of the hydrates. Ammonia is very particularly preferred. Ammonia, the amines (I) or the reagents releasing the ammonia or the amines (I), called aminating reagents hereinafter, can be used as pure substances or dissolved in organic solvents such as tetrahydrofuran, dioxane, toluene, N-methylpyrrolidone or water or mixtures thereof. The aminating reagents can be used either in excess or in the stoichiometric or less than stoichiometric amount, in each case based on the carbonyl group >C.dbd.O in the linear, alternating carbon monoxide/1-alkene copolymers. The preferred reaction of the linear alternating carbon monoxide/1-alkene copolymers with stoichiometric amounts or an excess of ammonia normally results, after hydrogenation, in polymeric polyamines with a primary amine functionality: (total of secondary amine functionality and tertiary amine functionality) molar ratio in the range from 1:1 to 1:10,000, preferably 1:2 to 1:100. The amine values, on which these ratios are based, are determined by titration as described in the examples. It is assumed on the current state of knowledge the following structural units III may be present in the polymeric polyamines obtainable in this way, with the structural units indicated by the indices a,b and c usually being distributed randomly along the polymer chain. ##STR2## Particularly good results are usually achieved when the aminating reagent:polyketone carbonyl group molar ratio is in the range from 1.1:1 to 20:1 or is, in particular, 2:1. Polymeric polyamines obtainable with stoichiometric amounts or with an excess of aminating reagents generally comprise less than 5% by weight carbonyl groups >C.dbd.O based on the polymeric polyamine, determined by the .sup.13 C-NMR spectroscopic method in CDCl.sub.3, at 20.degree. C., and less than 10% by weight, preferably less than 1% by weight, hydroxyl groups, based on the polymeric polyamine. If the aminating reagents are used in less than stoichiometric amounts, preferably in amounts in the range from 0.01 to 0.99, based on the carbonyl functionality >C.dbd.O in the polyketone, the resulting polymeric polyamines generally comprise an ether functionality, as 2,5-tetrahydrofurandiyl unit, detected by the .sup.13 C-NMR spectroscopic method, and hydroxyl groups. The amounts and molar ratios of the functional nitrogen and oxygen groups in the polymeric polyamine normally depend on the reaction conditions in the preparation thereof using less than stoichiometric amounts of aminating reagents. The total amount of chemically bonded oxygen in the polymeric polyamine:total amount of chemically bonded ether and hydroxyl oxygen in the polymeric polyamine molar ratio is normally in the range from 1:1000 to 1000:1, preferably in the range from 1:100 to 100:1. In the particularly preferred reaction of less than stoichiometric amounts of ammonia, preferably in amounts in the range from 0.1 to 0.99, based on the carbonyl functionality >C.dbd.O, with the linear alternating carbon monoxide/1-alkene copolymers, preferably carbon monoxide/ethylene copolymers, the resulting polymeric polyamines generally comprise, in addition to the primary, secondary and tertiary amine functionalities already described, an ether functionality, as 2,5-tetrahydrofurandiyl unit, and hydroxyl groups. The amounts and molar ratios of the functional nitrogen and oxygen groups in the polymeric polyamine also normally depend in this instance on the reaction conditions in the preparation of the polymeric polyamines using less than stoichiometric amounts of ammonia. The total amount of chemically bonded oxygen in the polymeric polyamine:total amount of chemically bonded ether and hydroxyloxygen in the polymeric polyamine molar ratio is normally in the range from 1:1000 to 1000:1, preferably in the range from 1:100 to 100:1. The primary amine functionality:(secondary amine functionality+tertiary amine functionality) molar ratio in the polymeric polyamine is normally in the range from 1:1 to 1:10,000, preferably in the range from 1:2 to 1:100. The polymeric polyamines obtainable with less than stoichiometric amounts of aminating reagents generally comprise less than 5% by weight, preferably less than 3% by weight, carbonyl groups >C.dbd.O, based on the polymeric polyamine, determined by the .sup.13 C-NMR spectroscopic method in CDCl.sub.3 as solvent at 20.degree. C. The number average molecular weight Mn determined by the gel permeation chromatography method of the novel polymeric polyamines is generally in the range from 100 to 1,000,000, preferably in the range from 100 to 500,000 and in particular in the range from 100 to 50,000. A suitable process for preparing the polymeric polyamines is to react the linear alternating carbon monoxide/1-alkene copolymers defined at the outset with ammonia or the amines R--NH.sub.2 (I) already defined, or with a reagent which releases ammonia or the amines (I) already defined, and subsequent hydrogenation. A two-stage process has proven particularly suitable, in the first stage of which the linear alternating carbon monoxide/1-alkene copolymers are reacted with ammonia or the amines R--NH.sub.2 (I) already defined or with a reagent releasing ammonia or the amines (I) normally at from 20 to 250.degree. C., preferably from 50 to 150.degree. C., under a pressure of from 100 to 20,000 kPa, without diluent or in water or organic solvents such as tetrahydrofuran, dioxane, toluene, N-methylpyrrolidone or cyclohexane. The hydrogenation is then carried out in a second stage, preferably without isolating and working up the reaction products from the first stage, generally in the presence of a hydrogenation catalyst under a pressure of hydrogen in the range from 100 to 35,000 kPa, preferably 1000 to 25,000 kPa, at from 20 to 250.degree. C., preferably from 100 to 220.degree. C. Suitable as hydrogenation catalyst are all those described for this purpose in D. D. Coffmann, J. Am. Chem. Soc. 76 (1954), 25 6394-6399; A. Sen, Adv. Polym. Sci. (1986) 125-144, but nickel (14% by weight)/aluminum oxide, ruthenium (0.5% by weight)/macroporous aluminum oxide or ruthenium oxide hydrate is preferably used. The amination and the hydrogenation are normally carried out until at least 5 mol % of the carbonyl groups >C.dbd.O in the initial polyketone have reacted, which can be checked by infrared spectroscopy. Preferred reaction times, both for the amination and for the hydrogenation, are in the range from 0.5 to 20 hours. The aminations can, as described above, be carried out with an excess or with stoichiometric amounts or less than stoichiometric amounts of aminating reagent, preferably ammonia, based on the carbonyl group >C.dbd.O in the linear alternating carbon monoxide/1-alkene copolymers. The novel polymeric polyamines can also be modified by conventional chemical methods. For example, the ammonium salts result from the reaction with acids such as carboxylic acids, ie. acetic acid, trifluoroacetic acid or else inorganic acids, such as sulfuric acid, hydrochloric acid or phosphoric acid. The novel polymeric polyamines can furthermore be alkylated with C.sub.1 -C.sub.25 -alkylating agents such as dialkyl sulfates, preferably dimethyl sulfate or diethyl sulfate, or else alkyl halides such as benzyl chloride. Generally used for this purpose are 0.1 to 2 mole equivalents, preferably 1 to 2 mole equivalents, of alkylating agent, based on the amine groups present in the polymer. Reaction of the novel polymeric polyamines with alkylene oxides, preferably ethylene oxide or propylene oxide, normally results in the corresponding alkoxylates, eg. ethoxylates. The novel polymeric polyamines are very suitable as surfactants and, in particular, as color transfer inhibitors, especially in detergents. The novel polymeric polyamines are particularly suitable for detergents and fabric conditioners which are free of anionic surfactants and those which have an anionic surfactant content of less than 2.5%, preferably less than 1.5%, particularly preferably 0 to 1%, of anionic surfactants. In a formulation free from anionic surfactants, the novel polymeric polyamines normally reach the effect plateau at a concentration of only 20 to 100 ppm in the wash or rinse liquor, whereas prior art polymers are used in concentrations of about 500 ppm. The novel polymeric polyamines are generally used in the fabric conditioners or detergents in amounts of from 0.05 to 10%, preferably 0.1 to 5.0%, particularly preferably 0.2 to 2.5%, based on the other ingredients of the formulation. The novel polymeric polyamines can advantageously be used as addition to liquid or solid detergent formulations or fabric conditioners which have a low or zero content of anionic surfactants. The composition of detergents and fabric conditioners can moreover be varied within wide limits. |
| PATENT EXAMPLES | This data is not available for free |
| PATENT PHOTOCOPY | Available on request |
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