JPH05502685A - Method for producing crosslinked polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Method for producing crosslinked polymer The present invention provides a new method for producing crosslinked polymers from linear hydroxy-functional polymers, and and novel hydroxy-functional polymers as starting materials for this process.

Cross-linked polymers are currently being used for example in materials (thermosetting polymers, rubber), coatings and supports. It is used as a holding material (gel-forming material) in many industrial fields. The crosslinked polymer is There are essentially two basic methods of synthesis for various classes of compounds that can be attributed to can. That is, can the polymer network be synthesized in one step from low molecular weight compounds? , or the already formed linear polymer can be cross-linked with a suitable polyfunctional reagent, etc. It is.

Suitable crosslinked polymers already exist for a variety of applications, but similar or different Further efforts are being made to discover new polymers with unique properties that can be easily produced on an industrial scale. Efforts continue.

If soluble hydroxy-functional polyalkyleneimines are moderately crosslinked, new It has been discovered that useful crosslinked polymers of the following types can be obtained.

The present invention provides a reagent having a plurality of groups capable of reacting with a hydroxy group, at least N- Soluble poly-N-acyl in which some of the acyl groups have hydroxy groups as substituents Regarding a method for producing a crosslinked polymer characterized by reacting it with an alkylene imine. It is something that

Poly-N-acylalkyleneimine is, in principle, a polyalkyleneimine. A compound of the general formula A prepared by unbinding with a boxylic acid or a carboxylic acid derivative It is a polymer (y=integer).

-(alkylene-N-), (A) R'-C=0 However, they are more commonly used because the alkylene group typically has 2 or 3 carbons. Cyclic imino ether shown by 2B, which is a molecular chain in which atoms may be substituted. Prepared by cationic polymerization.

These cyclic imino ethers are also known as δ-2-oxazolines or It is known as Draw 4H-oxazine. Therefore, polyiminoether (polyiminoether The name oxazoline or polyoxazine) has been coined.

A soluble polycarbonate having a hydroxyl group in the substituent R or some of these substituents N-acylalkyleneimines are used in the method of the invention. For example, they are Poly-N-acylalkyl imine having an acetoxy group as a substituent on the acyl group [Levy (A, Levy) and Lit (M, Lit) obtained by saponification T), J Polym Sci, A1.6.1 883-1894 (1968), and U.S. Pat. No. 3.483.145]. soluble The characterization of these polymers as a It doesn't mean to be restricted. Its function is simply to remove these polymers, which are generally solvents. to distinguish them from crosslinked polymers which do not dissolve in water and swell at most in solvents. 1-1 00 mol% of a cyclic iminoether of formula I and 99-0 By copolymerization with mol % of at least one cyclic imino ether of formula II It is preferred to use soluble poly-N-acylalkylene imines prepared by Specifically, Formulas I and 11 have the following structures.

Formula I: N-CRIR2 HO-CHR-M-Z Here the abbreviations have the following meanings: R = alkyl or alkenyl containing 1 to 12 carbon atoms, or aryl; M = alkylene, alkenylene, ali whose molecular chain may contain ether oxygen a divalent group having 1 to 12 carbon atoms selected from -lene and alkarylene groups; group or a direct bond; R and M further represent a hydroxyl group and/or a 1-3 carbon May be substituted with an alkoxy group having an elementary atom: Z=direct bond or CR5R 'Group; R1 to Rg = mutually independently H, alkyl or aryl having 1 to 8 carbon atoms Group: Formula II: N-CRIR2 0-CR3R4 Here the abbreviations have the following meanings: R7=alkyl, alkenyl, aryl, alkary having 1 to 21 carbon atoms t or R''-0-(CHzCHzO-)-R'- (where x=O~2, R"=C,-, alkyl, R"=C,-, alkylene); Z, R1-R'=same meaning as in formula I, but independent therefrom.

15.1 to 100 mol%, in particular 20 to 98 mol% of at least one of formula I species cyclic iminoether and 84.9 to 0 mol %, especially 80 to 2 mol % of formula II Polymers obtained by copolymerization with at least one cyclic imino ether represented by Particularly preferred is ly-N-acylalkyleneimine.

Most of the cyclic iminoethers are known and can be prepared using known methods, such as German patent 1. No. 6 70 012, German Patent No. 14 45642 or earlier application Patent No. 39 14 155.39 14 133 and European Patent Application 88 All manufactured by 118090.5. The following is a circular i 2-(2-hydroxypropoquinphenyl)-oxa, which is an example of a minoether Zoline, 2-(1-hydroxyethyl)-oxazoline, 2-(2-hydroxy propyl)-dihydroxazine, 2-(1-hydroxybutyl)-oxacyly 2-(3-hydroxybutyl)-dihydroxazine, 2-(1-hydroxybutyl) Cypentyl)oxazoline, 2-(3-hydroxypentyl)oxazoline, 2-(3-hydroxyheptyl)-oxacillin, 2-(3-human 0quinnonyl )-oxacillin, 2-(α-hydroginebenzyl)-oxazoline, 2-(4 -hydroxyethyl)-dihydroxazine, 2-(1~hydroxy=3- methylbutyl)-oxacillin, 2-(11-hydroxyheptadecyl)-oxacillin Sazolin, 2-(11-hydroxy-9-hebutadecenyl)-oxacillin, 2 -(9-hydroxy-10-methoxyhebutadecenyl)-oxazoline, 2-[ 13,14-(hydroxy,methoxy)-heneicosyl]-ogisazoline.

The following is an example of a cyclic imino-tyl of formula II: 2-ethyloxapuri 2-hebutyloxazoline, 2-(2-ethylpentyl)-oxazoline, 2-octyloxazoline, 2-nonyloxazoline, 2-undecyloxadi 2-pentadecyloxazoline, 2-heptadecyloxazoline, 2-(8 -hebutadecenyl)-oxazoline, 2-(8,11-heptadecagenyl)- Oxacillin, 2-hebutyl-3-methyloxazoline, 2-phenyl-4-methyl Tyloxazoline, 2-phenyloxazine, 2-(4-tert-butylphenyl) 2-(4-chlorophenyl)-oxacillin, 2-(4-chlorophenyl)-oxazoline, 2-(2 -oxopropyl)-oxazine, 2-(2,5-oneoxahexyl)-oxa Silin, 2-(2,5,8-trioxanonyl)-oxacillin.

The polymerization of iminoethers can be carried out by methods known per se, for example German Patent No. 12065. 83, U.S. Patent No. 3.458.456, or earlier German Patent Application No. 39.0 0859.2. In contrast to the disclosure of U.S. Patent 3.458.456 Even if the iminoether corresponding to formula I is used in considerably higher molar amounts, the The poly-N-acylalkyleneimine produced in the reaction is not insoluble.

At least 4 of the substituents R1 to R6 in formula (■) and/or H are hydrogen atoms; , the others are C1-3 alkyl cyclic iminoethers made from poly-N -Ano alkyleneimines are particularly preferred for the method of the invention. Furthermore, formula I and Z in and/or II is preferably a direct bond, in other words the monomer is δ-2- It is an oxazoline.

Among these monomers, those having the following substitution patterns are particularly preferred.

R,=CH3, R2-R,=H R3=CH3, C2H5 or phenyl: R1, R2 and R,=H all positions Most particularly preferred are poly-N-acylalkyleneimines in which the substituents R1 to R6 are hydrogen. Yes.

If the poly-N-acylalkyleneimine is a copolymer, the selected polymerization conditions Depending on their It is produced by conventional methods as a lock copolymer. is almost always a statistical polymer - is preferred, but all forms are suitable for the method of the invention. Poly-N-acyl The molecular weight of kylenimine can vary over a wide range, e.g. between 1.000 and 1,000,000. , preferably freely selected between 3.000 and 50.000.

The above soluble hydroxy-functional poly-N-acylalkyleneimine has been reported so far. It has not been. Even a few percent of hydroxy-functional cyclic imino ether can be polymerized to provide a crosslinked and therefore insoluble poly-N-acylalkyleneimine. Previously known [U.S. Pat. No. 3,458,456 and Levy A. and Litt (M.

L 1tt), Polym, Sci (J, Polym, Sci,) A1. 6゜1883-1894 (1968)). However, the im If a noether is used, a soluble poly-N-acylalkyleneimine is produced. I found out that it can be done. The invention therefore relates to this compound. This compound is 15.1 to 100 mol %, preferably 20 to 98 mol % of the cyclic group of formula I 84.9 to 0 mol, preferably 80 to 2 mol % of the formula II It is produced by copolymerization with a cyclic imino ether and has 16 to 22 carbon atoms. 20% by weight or more of monomer units having acyl groups of unsaturated aliphatic carboxylic acids Borianolalkylene according to earlier German patent application No. 39 00 859.2 containing It is a poly-N-acyl alkylene imine containing no imine. about other things The explanation given above referring to poly-N-anosialkyleneimine again Applicable. Regarding the preparation of new compounds, the prior application specifically included in the subject matter of the present invention Reference is made in particular to the disclosure of German patent application 39 00 859.2. Especially preferred The compounds are 2-hydroxypropionic acid, 3-hydroxybutyric acid, 4-hydroxy Octanoic acid, 12-hydroxystearic acid or 9゜10-(hydroxymeth) xy) having an acyl group of stearic acid, and R7 is 1 to 21, preferably It is an alkyl group or a phenyl group having 2 to 17 carbon atoms.

The reagents required for the crosslinking reaction must contain at least two functional groups that can react with hydroxyl groups. , preferably a low molecular weight compound.

Examples of such groups are anhydride groups and acid chloride groups. The reactivity of these groups is It is important in determining the reaction conditions of the method. Crosslinking to existing hydroxyl groups The amount of reagent used determines the degree of crosslinking, and the upper limit for the degree of crosslinking is poly-N-acylalkyleneimide. It is also determined by the density of hydroxyl groups in the molecule.

Preferred crosslinking reagents for the method of the invention are polyisocyanates and aminopropylene. A plastic initial condensate, such as a phenol/formaldehyde initial condensate. Objects are also suitable.

Polyisocyanates are compounds of formula III.

A(-NGO). (III) where A is an aliphatic, aromatic or araliphatic group having 4 to 40 carbon atoms; , n is the free valence of various carbon atoms and takes a value of 2.3 or 4. child These polyisocyanates are usually prepared by reacting with CO’C1□ from the corresponding amine. It is a known compound produced.

They preferably have 6 to 26 carbon atoms in the A part of the molecule. on this subject Further information can be found in Kirk-Othmer's encyclopedia. Encyclopedia of Chemical Technology Chemical Technology), 3rd edition, vol. 23, p. 586 (19 It is found in literature such as 1984). Examples of suitable polyisocyanates are N, N’ , N”-tris-(ω-isocyanatohexyl)-biuret, 2,2.4- Trimethylhexamethylene-1,6-diisocyanate, 1,6-hexamethylene lylene diisocyanate, 2.4-) lylene diisocyanate, 4.4゛- and/ or 2.4°-phenylmethane diisocyanate, 4.4°-nnochlorhexyl silmethane diisocyanate and isophorone diisocyanate. Diiso Cyanates are particularly preferred for the purposes of this invention. Alternatives to polyisocyanates of formula III Alternatively, so-called masked polyisonoanates have been used with similar success. Ru. The masked polyisocyanate is a polyisocyanate of formula III. It is an addition compound with The addition reaction is carried out in the same manner as for polyisonoanate. Average of about 500-5.000 A long-chain α,ω-diol with a molecular weight and an excess of diisocyanate of formula A So-called prepolymers terminated with isocyanate groups, which are usually produced from It is suitable.

The reaction between isocyanate III and poly-N-acylalkyleneimine Conditions normally used for the reaction of alcohols with isocyanates, i.e. from about room temperature to about 1 The reaction proceeds smoothly at a temperature of 60°C and a reaction time of about 1 to 10 hours. However, iso Depending on the reactivity of the cyanate and alcohol components, reaction conditions may also vary between these limitations. It may be more or less than that. The reaction is carried out in a suitable aprotic solvent, e.g. aromatic carbon. carried out in the presence of hydrocarbons, chlorinated hydrocarbons, esters or ketones, generally water It is carried out in a state of old age. However, the crosslinking reaction is preferably carried out without solvent. . The reaction is carried out using catalysts typically used for the reaction of alcohols with isocyanates. Tin compounds such as dibutyltin dilaurate, or 1,4-diazabicyclo[2 ,2,2]-octane. Progress of reaction is unreacted Determination of isocyanates, e.g. reaction with excess dibutylamine in toluene and followed by back titration with HCI.

Generally, more polyisomer than is needed for complete reaction with the supplied hydroxyl groups. Cyanate is not used for crosslinking. In many cases, especially when minimal crosslinking is desired, and/or if the final product is intended to still contain hydroxyl groups. , it is sufficient to use less than an equivalent amount of polyisocyanate.

The preferred aminoplastic precondensate as a crosslinking reagent is a lower alcohol. Formaldehyde and various amides, preferably urea, which may be etherified and/or condensation products with melamine.

The characteristic structure of these products, which are commercially available in various forms, is that between the amide nitrogen atoms methylene bonds, methylol groups attached to nitrogen, and optionally alkoxymethyl It is the basis. Further information on this can be found in the literature, e.g. Ullmanns Enc yklopadie dertechnischen Chemie), 4th edition , Vol. 7, p. 403 (1974).

The components are first mixed using a suitable solvent such as an aromatic hydrocarbon or a suspending agent such as water. However, the initial condensate of poly-N-acylalkyleneimine and aminoplastic The reaction between is preferably carried out without a solvent. The actual crosslinking reaction takes place at a fairly high temperature. , preferably in the range from 100 to 220°C, and generally lasts from 5 to 45 minutes.

The reaction between aminoplastic initial condensate and poly-N-acylalkyleneimine is It does not follow any fixed stoichiometric ratio. Therefore, the ratio between the reactants is determined by the desired final product. can be freely selected from a wide range depending on the nature of the The weight ratio of 1 to 0.2 is poly- Normally, the hydroxyl group content in N-acylalkyleneimine is 15 mol% or more. Yes, weight ratio 0°7 to O25 (initial condensate to poly-N-acylalkyleneimine) ) are preferred, but ratios above or below these limits can also be applied.

The final product of this method is a highly elastic product that can swell in solvents due to the low crosslinking rate. ~ It is a rigid material. They are extremely suitable as materials and can be molded if required. It can also be manufactured directly inside. They form a durable and tightly adhering coating. It is highly suitable as a coating for hard surfaces.

Example A. Preparation of hydroxy-functional poly-N-acylalkyleneimines For the purpose of the present invention A suitable poly-N-acylalkyleneimine is combined with p-toluenesulfonate as a catalyst. The cyclic imino ether of formula II and the cyclic imino ether of formula II in the presence of It was produced by cationic polymerization in bulk with a cyclic imino ether. after that , the iminoethers are mixed in a given ratio at room temperature or just above their melting point, and the catalyst is A small amount of p-toluenesulfonic acid methyl ester was added with stirring. Afterwards, the resulting mixture was heated at 160° C. for 30 minutes.

When using iminoethers with relatively low boiling points, polymerization takes a correspondingly long time at the boiling point. The conversion was always completed, even though the temperature was below that point. iminoacetate used for polymerization Tables 1 and 2 show the industrial carboxylic acids. European Patent Application No. 88 118 090.5, German Patent No. 39 14 133 and German Patent No. 30 14 155. Polymerization is generally It was carried out in batches of about 100 g. A product is produced that is solid at room temperature and the process of the invention was used without further purification. Polymers were characterized by their respective molecular weights as a weight average by gel permeation chromatography using polystyrene as a standard. measurement). Polymerization examples and molecular weights of the products are shown in Table 3.

Table 1: Cyclic imino ether NO represented by formula I, molecular weight of imino ether Rubonic acid base nRMal 323 Ricinoleic acid 2 C6HI3 CIQ III8a2 337 Ricinoleic acid 3 CJ+3 C+oLga3 401 12,13-(human o+), itoquino)-2 mixture behenic acid a4 356 9.10-(human 0 kino, metquin)-2 mixture stearic acid a5 325 12-hyde σki/steary/acid 2 CJ+3 Cl0I12 ゜a6　115　DL-Lactic acid　2　CH3-Table 2 Cyclic imitation shown by formula II Noether No. Molecular weight Iminoether carboxylic acid base n R7bl 309 Stearic acid 2 C17H35b2 309 Isostearic acid 2 Cl7H35b3 300 Soybean oil fatty acid 2 Mixture b4 225 Rau Phosphoric acid 2 C2H3b9 239 Lauric acid 3 C2H3b6 197 Neoisononylcarboxylic acid 2 CJ.

(CHversatic acid) by 169 Caprylic acid 2 CJ+sb8 99 Propionic acid 2 C2 H3b9 147 Benzoic acid 2 C6E15blo 178 3.6.9-) Rioki Decanoic Acid 2 C6H+ 303bll 365 Behenic Acid 2 C2 1EI43 Table 3: Poly-N-acyl alkylene imine imino ether catalyst molecular weight Examples Formula I Formula II Molar ratio Mol% 1 a3 - 1 40.000 2 al b9 1:2 1 22,0003 a3 b5 1:1 1 34 ,0004 a3 b4 2:1 1 35,0006 a5 b4 1:1 1 30,0007 a2/al b2 (1:1): 0.5 1 34,00 08 a6 b9 1:1 1 15.0009 a5 b8 1:2 1 1 8,00010 a5 b8 1:9 0.5 26.00011 a5 b9 /b8 1:(0,25:3) 1 15.00012 a5 - 1 39. 000 13 a3 bll 7:3 0.5 123.00014 a4 b3 4: 1 1 38.00015 a4 0.15 255.00016 a5 bl o 2:1 0.6 48.00017 a3 b9 1:1 1 29.00 018 a3 b9 1:3 1 22,00019 a3 b7 1:3 1 26.00020 a3 b7 1:1 1 30.00021 a4 b7 /b6 2: (1:1) 2 14.00022 al b9 3 near 1 2 1,00023 a6 b2 1:8 3 11,500B, poly-N-acyl Cross-linking with aminoplastic initial condensate of alkyleneimide In these examples, crosslinking is carried out on stretched steel plates, which makes the plates A thermosetting lacquer coating was obtained on top.

70% toluene solution of poly-N-acylalkyleneimine or these polymers A 55% aqueous dispersion of melamine resin [Cymel 301, American Cyanamid (product of American Cyanamid)] and 7:3 weight Mix in quantitative ratio (based on solvent-free product) and knife coat the resulting mixture was applied to the plate. The aqueous dispersion is best prepared using a 33% isopropanol solution of the polymer. First mix, then add 2.5 times the amount of water (based on the polymer) while stirring. Manufactured. Next, add a mixture of isopropanol and water until a 55% water dispersion remains. It was removed from there. The coated plates were air-dried at room temperature and then placed in a thermostatic oven with air circulation for 25 minutes. The film was crosslinked by heating at 160°C. The next day, the pendulum hardness of the lacquer film was D. Measured according to IN 53 157. The results listed in Table 1 below indicate that the coating Shows excellent hardness.

Table 1: Crosslinking on steel plate Po1) -N-Anoral solution or film thickness Example N of pendulum type example Solvent of O dispersion μm Hardness 24 1 Toluene 30 120 25 6 Toluene 30 106 26 9 Toluene 50 1Q2 27 11*Wed 40 113 28 17 Toluene 40 l33 29 18 Toluene 90 94 *Poly-N-acylalkyleneimine: weight ratio of aminoplastic initial condensate 41 Crosslinking of C poly-N-acylalkyleneimine with polyisocyanate This cross-linking reaction is also carried out on steel plates in order to obtain a coating film that adheres strongly using this method. The reaction mixture was knife-coated as a film on top. In this example, mixed equivalents of poly-N-acylalkyleneimine (based on hydroxyl groups) and 4,4'-diphenylmethane diisocyanate (MDI) or caprolac Tam masked diisocyanate (Grillbond) IL6 (EMS-Chemie), equivalent weight 238]. coated pre The coating was placed in a heating cabinet with air circulation at 160°C for 25 minutes to crosslink the film. . The next day, the properties of the lacquer film were determined by pendulum hardness (DIN 53 157) and impact depression. (ASTM-D 2795-69) and crosshatch adhesion strength DIN It was measured in the format of 53 151). The higher the pendulum hardness and impact indentation values, the higher the The higher the hardness, the greater the hardness and the better the flexibility of the coating. Crosshatch adhesion strength is 0 (adhesion is Visual evaluation was made on a scale of 4 (best) to 4 (poor adhesion).

Table 2 2 Bridge on steel plate Poly-N-Anol Shock Alkylene imine polyiso film thickness pendulum type indentation cross hatch example Example of Noanate μm Hardness inch x Bod adhesion strength 30 22 MD I 60 160 > 80 031 22 Grill-40150 > 80 0 ond L6 32　1　Grill-50100>80　0ond L6 abstract Poly-N-acyl in which at least some of the N-acyl groups have hydroxyl substituents Reacting an alkyleneimine with a reagent that has multiple groups that can react with hydroxyl groups. A new polymer is created. First polyisocyanate and aminoblastinc Phase condensates are suitable reagents. New polymers in materials and coatings for hard surfaces Can be used as

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Claims (14)

[Claims] 1. Reagents containing multiple groups capable of reacting with hydroxyl groups are Poly-N-acylalkylene with some hydroxyl groups as substituents A method for producing a crosslinked polymer, characterized by reacting it with an imine. 2. The poly-N-acylalkyleneimine used is 1 to 100 mol % of formula I 99 to 0 mol % of a cyclic imino ether of formula II 1. Obtained by copolymerization with an ether, formulas I and II have the following structure: Method of writing: Formula I: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R=alkyl or alkenyl having 1 to 12 carbon atoms, or aryl; M=alkylene, alkenylene which may contain ether oxygen in its molecular chain; having 1 to 12 carbon atoms selected from arylene and alkarylene groups divalent group or direct conjugation; R and M further represent a hydroxyl group and/or 1- Optionally substituted with an alkoxy group having 3 carbon atoms; Z=direct bond or CR5R6 group; R1 to R6 = mutually independently H, alkyl or aryl having 1 to 8 carbon atoms Le. ] Formula II: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R7=alkyl, alkenyl, aryl, alkary having 1 to 21 carbon atoms rule or R8-O-(CH2CH2O-)xR9- group (where x=0-2, R6=C1 -3 alkyl, R9=C1-3 alkylene); Z, R1-R6=same meaning as in formula I, but independent therefrom. ]. 3. 3. The method according to claim 2, wherein Z in formula I and/or formula II is a direct bond. 4. according to claim 2, wherein R1 to R6 in formula I and/or formula II are hydrogen atoms; Method. 5. Reagents that can react with hydroxyl groups include polyisocyanates, masked poly The claim is an isocyanate or a prepolymer terminated with isocyanate groups. 5. The method according to any one of 1 to 4. 6. Reagents capable of reacting with hydroxyl groups must be aminoplastic precondensates. 5. The method according to any one of claims 1 to 4. 7. 15.1 to 100 mol% of cyclic imino ether of formula I and of formula II obtained by copolymerization with 84.9 to 0 mol% of cyclic imino ether, and these The formula is an unsaturated aliphatic compound having the structure shown in claim 2 and having 16 to 22 carbon atoms. N-acyl containing 20% by weight or more of monomer units having an acyl group of a carboxylic acid Poly-N-acyl alkylene imine that does not eat alkylene imine. 8. 20-98 mol % cyclic amino ether of formula I and of formula II 8. The polymer according to claim 7 obtained by copolymerization with 80 to 2 mol% of a cyclic amino ether. Li-N-acylalkyleneimine. 9. The number of substituents R1 to R6 in formula I and/or formula II, preferably in both 7. At least four of the atoms are hydrogen atoms, and the others are C1-3 alkyl atoms. is the poly-N-acylalkyleneimine described in 8. 10. Z in formula I and/or formula II, preferably in both, is a direct bond The poly-N-acylalkyleneimine according to claim 7 or 8. 11. R1 to R6 in formula I and/or formula II, preferably in both, are hydrogen atoms. 11. The poly-N-acylalkyleneimine according to claim 10, which is a poly-N-acylalkyleneimine. 12. The HO-CHR-M- group in formula I is 2-hydroxypropionic acid, 3-hydro Roxybutyric acid, 4-hydroxyoctanoic acid, 12-hydroxystearic acid or Claims that it is an alkyl group of 9,10-(hydroxy, methoxy)-stearic acid 8. Poly-N-acylalkyleneimine as described in 7 or 8. 13. R7 in formula II has 1 to 21 carbon atoms, preferably 2 to 17 carbon atoms The poly-N-acyl according to claim 7 or 8, which is an alkyl group or a phenyl group. Alkylene imine. 14.1,000-1,000,000, preferably 3,000-50,000 The poly-N-acylalkyleneimine according to claim 7 or 8, having an average molecular weight of .