DE1817309A1 - Basic and cationic ethylene copolymers - Google Patents

Abstract

Statistic copolymers comprising units (A) -(CH2-CH2)- (B)-(CH2-CH)- and (D) -(CH2-CH)- the proportion of (A) being 5-99, pref. 52-96, wt.%, (B) 0.2-88, pref. 1-41.5 wt.%, (D) 0.13-88 pref. 0.7-31 wt.%. Alternatively, the copolymer may also contain units (C) -(CH2-CR)- (Z=OH), in which case the composition is (A) 51-84 wt.%, (B) 0.4-41%, (C) 0.7-14%, (D) 0.5-31%. The copolymers have mol. wt. 103-105 and maybe used, in form of free bases, as catalysts for resins, or antistatic agents; their salts are useful as emulsifiers or thickening agents. Prodn. is by acidic hydrolysis or alcoholysis of the starting polymers in homogeneous or heterogeneous phase. Starting polymers are obtd. by copolymerising in known manner, N-vinyl-N-methylformamide, ethylene and opt. one or more ethylenically unsatd. radical-polymerisable cpds. e.g. vinylchloride, vinylmethylether, pref. vinylacetate or ethyl- or methyl-(meth)acrylate.

Description

Basic and cationic copolymers of ethylene and process too Their production polymer bases and polyelectrolytes with polycations are significant more difficult to access than polymeric acids and polyelectrolytes with polyanions. However, basic and cationic polymers have considerable technical interest.

From US Patent 3,207,732 are copolymers of ethylene and N-vinyl-N-methylacetamide known. However, these are not basic compounds. A saponification to such with cleavage of the acetyl radical can, if at all, only with difficulty and only with very small sales.

Furthermore, due to the German interpretation document, 1.167.o27 was a Process for the polymerization of open-chain, tertiary N-vinylamides with others free-radically polymerizable, olefinically monounsaturated compounds are known been.

The patent claim of this protection right also formally includes the Production of copolymers from ethylene and N-vinyl-N-methylformamide building blocks; any information about the properties, in particular about the saponifiability, however, this DAS is not made at any point.

One had to expect, therefore, that copolymers of ethylene and N-vinyl-N-methylformamide building blocks the same or at least very similar behavior as copolymers of ethylene and would show N-vinyl-N-methylacetamide building blocks.

The present application relates to a process for the preparation of basic and cationic copolymers by solvolysis of polymeric compounds at elevated temperature, which is characterized in that the solvolysis reaction is carried out on polymeric starting compounds which are composed of the randomly arranged basic building blocks and if necessary consist, where Z = chlorine, -COOR ', -OCOR1, -OR', preferably -OCOCH3, R = H or -CH3 and R '= -CH) or -C2H5.

Based on the prior art, it was surprising that when used of copolymers containing the N-vinyl-N-methylformamide & round building block, the solvolysis reactions even under mild and economically viable conditions Times run out.

The copolymers according to the invention are preferably prepared by acid hydrolysis or alcoholysis of the starting polymers in homogeneous or heterogeneous Phase. All substances that boil above 60 ° C. are suitable as the reaction medium and are not themselves saponified under the reaction conditions. To be favoured Water, alcohols, ethers, aliphatic and aromatic hydrocarbons and chlorinated hydrocarbons. The choice of solvent is made by the composition of the copolymer and by the fact that the reaction proceeds faster in a homogeneous phase than in a heterogeneous one, certainly.

Copolymers with more than 35% by weight of N-vinyl-N-methylformamide can be used saponify well in an aqueous system. Copolymers with 10-35% by weight of N-vinyl-N-methylformamide are advantageously implemented in an aqueous alcoholic system, e.g. methanol, May use methanol, propanol, n-butanol, or 2-ethylhexanol.

With smaller contents of N-vinyl-N-methylformamide than lo wt.

in the copolymer it is favorable, in the anhydrous alcoholic system to saponify, aliphatic and aromatic hydrocarbons as solubilizers, such as iso-octane, benzene, toluene or chlorinated hydrocarbons such as carbon tetrachloride or chlorobenzene, can be added.

The concentration of the copolymer to be saponified in the reaction medium is generally between 20 and 60% by weight.

In principle, concentrations are also outside the specified range applicable, but at concentrations below 20 wt.

the consumption of diluent too high and at over 60% by weight die The viscosity of the solutions becomes unfavorably high.

Mineral acids, such as halogen compounds, are suitable as catalysts for the solvolysis. Sulfuric acid, nitric acid, phosphoric acid (ortho-, meta-, poly-phosphoric acid) and organic acids such as aliphatic or aromatic sulfonic acids. For example may be mentioned: methanesulphonic acid, p-toluenesulphonic acid.

The addition of these acids to the saponification batch can be done undiluted take place in solid, liquid or gaseous state; but you can also use Form of their aqueous or alcoholic solutions are added.

The catalyst concentration will depend on the content of the copolymer N-vinyl..N-methylformamide determined. Since the catalyst is off as a result of the salt formation the system is removed, one uses a content of the copolymer of N-vinyl-N-methylformamide or an at least stoichiometric amount corresponding to the proportion to be saponified of acid; in general, an excess of 50% is used. The saponification can can also be catalyzed under alkaline conditions; because of side reactions occurring this is. However, the procedure is less suitable.

The reaction temperature is between 50 and 200 ° C., preferably between 60 and 16o0C. In general, the system is refluxed, see above that the temperature depends on the choice of reaction medium. However, it can be beneficial be, with low-boiling reaction media in the closed system at higher Saponify temperature under autogenous pressure.

If the reaction system is homogeneous, stirring is not absolutely necessary, but functional; when working in a heterogeneous phase, it is necessary to stir.

The reaction times depend on the composition of the starting polymer, the temperature and the desired degree of saponification; in general they are 2 to 200 hours, preferably 2 to 30 hours.

The implementation of the contained in the starting polymer Basic building blocks for the - Basic building blocks can, depending on the saponification conditions, be between 10 and 90% by weight, preferably between 20 and 80% by weight.

The reaction products can be isolated in the form of their salts, E.g. simply by evaporation of the resulting saponification solutions.

To obtain the free bases, you put the reaction mixture with aqueous alkali or ammonia weakly alkaline; organic solvents present are made by distillation or water.

removed by steam distillation.

Polymeric amines from starting polymers with less than 70% by weight of N-vinyl-N-methylformamide basic building blocks fall in pure powder form and are isolated by filtration. Polymers Amines from starting polymers with more than 70% by weight of N-vinyl-N-methylformamide basic building blocks are soluble in water; after removing the low molecular weight salts by dialysis they can be isolated by evaporation, spray drying or freeze drying of the solution will. The use of anion exchangers to obtain the free bases is possible.

The starting polymers for producing the copolymers according to the invention consist of - basic building blocks and Basic building blocks that are present in a statistical arrangement [= poly-ethylene-co (N-vinyl-N-methylformamide)].

The content of basic building blocks (A) in the starting polymer is 5-98, preferably 50-95% by weight and that of (B) 95-2, preferably 50-5% by weight J corresponding to nitrogen contents of 0.3-15.6% by weight.

According to the invention, the starting polymers which can also be used are those which, in addition to the basic building blocks (A) and (B), are also the basic building blocks (C) contain (where Z and R have the meanings given above they consist of 4-78, preferably 49-78% by weight (A), 95-2, preferably 50-2% by weight (B) and 1-20% by weight (C).

The conversion of these terpolymers with acid also takes place on the substituents Z saponification reactions or transesterification reactions take place; thus, for example, the -OCOCH3 residues Converted to OH groups.

The production of the starting copolymers takes place in pressure vessels in batch or continuous process, at elevated pressure and temperature and in the presence of oxygen and / or free radical forming compounds, by copolymerization of N-vinyl-N-methylformamide, ethylene and optionally one or more other mono-ethylenically unsaturated.

th radical polymerizable compounds, such as vinyl chloride or Vinyl methyl ether; preferably vinyl acetate or AcrylaMuremethileater or -Mthvlester or the analogous methacrylic acid-10 derivatives used.

The copolymerization can take place in bulk, but preferably in the presence of solvents or diluents as solvent or precipitation polymerization and be carried out as emulsion or suspension polymerization. As a solution and diluents, all liquids that do not polymerize are suitable prevent and do not react with the monomers, especially aliphatic and aromatic hydrocarbons, alcohols, ketones, halogenated hydrocarbons, Esters, ethers, amides, for example: hexane, benzene, toluene, methanol, i-propanol, tert-butanal, acetone, methyl acetate, ethyl acetate, tetrahydrofuran, dioxane, Dimethylformamide, dimethyl sulfoxide, water and their mixtures.

The amount of solvent is chosen so that the total monomer concentration of the monomers is between 10 and 90% by weight, preferably 20-70% by weight.

Oxygen or all substances are used to initiate the polymerization suitable that form free radicals under the reaction conditions, e.g. peroxides, Acyl peroxides, peresters, hydroperoxides, aliphatic azo compounds and persulfates, Peroxides such as di-tert-butyl peroxide or azo compounds are particularly suitable, such as azodiisobutyronitrile or persulfates such as ammonium persulfate. The initiators are in amounts of o, ool -5, preferably 0.05-2 wt.%, Based on the polymerized Monomers, which corresponds to the yield of copolymer, are used.

The polymerization is expediently carried out at temperatures of 30-250 ° C, preferably 60-2000C.

The pressure range in which Xthylene and N.Vinyl-N-methylformamide polymerize is very broad and is between about 2 and 3000 at, preferably 10 and 2000 at.

Which pressure is applied in detail depends on the desired Properties of the copolymers. In particular, the combination of the copolymers determined by the ratio of the monomer concentration, the ethylene concentration directly to the print is proportional. At a given temperature it hangs the ratio of the basic building blocks in the copolymers, the molecular weight and the crystalline parts differ largely from the pressure.

To set one at a given temperature and pressure desired low molecular weight can regulate the polymerization approach, such as hydrogen, propane, cyclohexane, chlorinated hydrocarbons, i-propanol; added will.

The limiting viscosity number serving as a measure of the molecular weight [#] (intrinsic viscosity) is used in the starting polymers with less than 50% by weight N-vinyl-N-methylformamide basic building blocks in the polymer in toluene at 850C> with 50-80% by weight in methylene chloride at 250 ° C. and with more than 80% by weight in water 250C measured in the Ubbelohde capillary viscometer; it is at least o, o5 (dl / g), preferably 0.05-1.5 (dl / g).

The specified viscosity limits correspond to the number average of the Molecular weight (Mn) of at least 1,000, preferably 1,000 to 1,000,000; these Values are as a first approximation with the [#] - Mn relationship for high pressure polyethylene: Xylene io o> 738 [#] 85 ° C = 3.36 x 10 @@ Mn @@@@@. Mn is that number average molecular weight.

The breadth of the molecular weight distribution of the starting copolymers> expressed by the ratio Mw / Mn can be between 1.5 and 20, preferably 2 - lo, lie; generally the value is between 2 and 4, with lower values mean greater uniformity than greater values. Mw is the weight average of the molecular weight, determined e.g. by light flux, Mn is the number with.

part of the molecular weight, determined by the osmotic method.

Mw / Mn can be determined by the absolute level of the temperature, temperature control, Sales and the addition of compounds that have a regulating effect, within certain limits to be influenced.

The copolymerization parameters (reactivity ratios) rl and r2 (for For definition see Brandrup / Immergut, Eds. Polymer Handbook, Interscience publishers, S. II 141) the copolymerization of N-vinyl-N-methyl-formamide and ethylene were approximate determined to be rl = 1.2 + 0.2 (N-vinyl-N-methylformamide) and r2 = 0.5 + 0.2 (ethylene).

The parameters can change because of the difficulty of the ethylene concentration to be specified exactly in the reaction mixture, can only be determined approximately. These found However, the copolymerization parameters are in satisfactory agreement with the Q and e values (for definition see Brandrup / Immergut, Eds. Polymer Handbook, Intersience publishers 1966, II 341). For N-vinyl-N-methylformamide these are: Q = o, o57, e = -l, lo (own values, determined from the copolymerization of N-vinyl-N-methylformamide / vinyl acetate) and for ethylene: Q = o, ol5, e = -0.20 (Brandrup / Immergut Eds.

Polymer Handbook, Interscience publishers, New York 1966, II 356).

The copolymerization parameters show that N-vinyl-N-methylformamide polymerized to a somewhat higher proportion in the copolymer than its proportion in the Reaction approach corresponds.

Despite this preferred incorporation of N-vinyl-N-methylformamide corresponds the system N-vinyl-N-methylformamide / ethylene is much more the azeotropic system vinyl acetate - xethylene than, for example, the systems (meth) acrylic acid ester / ethylene, in which r1 >> r2.

The starting copolymers are therefore relatively small chemical non-uniformity; by suitable process steps, such as adding N-vinyl-N-methylformamide during the reaction as the reaction progresses, chemical uniformity can be increased.

The manufacturing conditions and some properties are in table 1 listed.

Table 1: Conditions of manufacture and properties of polyethylene-co- (N-vinyl-N-methylformamide) Polymerization polymer properties conditions @@ lym @@@@ g @@@@@@@ @@@ Copolymer No. Pressure Temperature N-content VMFA- [#] 2) Density7) (atm) (° C) (wt.%) Content1) (dl / g) (g / cm3) (% by weight) 1 500 145 1.1 6.7 o, 569 0.907 2 2000 140 1.7 10.3 0.610 o, 931 3 500 140 3.2 19.1 0.210 0.928 4 - 500 140 3.1 18.8 0.391 0.929 5 500 140 5.6 34.2 0.180 0.942 6 40 70 11.9 72.5 0.2013) 7 lo 7o 15.6 95, o 0.2204) 8 500 140 2.3 14 VMFA51 @ 0.259 0.929 VA 9 500 140 2.6 16.6 0.505 0.910 VMAA 6) 10 500 140 4.4 31.8 0.203 0.935 VMAA 6) 1) VMFA = N-vinyl-N-methylformamide 2) [#] = intrinsic viscosity in xylene, 85 ° C. 3) in methylene chloride, 25 ° C. 4) 4) in water, 250 ° C. 5) VA = vinyl acetate 6) VMAA w N-vinyl-N-methylacetamide 7) the density was determined by the swimming method certainly.

The saponification products according to the invention consist of the basic building blocks (A), (B), (D) and (D '), the arrangement of the basic building blocks being statistical, and can be characterized as follows: (A) (B) (D) a) Poly + CH2-CH24 CH2 C + cH29H 23 CHO CH3 or if the basic building block (D) is in salt form: (A) (B) (D1) CH b) Poly + CH2-CH2 + CH2-9H4 NI2 CH3 CHO C3 H CH) XCHO) 2 where X is the anion of the acid serving as the saponification catalyst, as defined above.

The content of basic building block (A) is 5 - 99, preferably 52 - 96% by weight, that of basic building block (B) o, 2 - 88, preferably 1 - 41.5% by weight and the of basic building block (D) 0.13-80, preferably 0.7-31% by weight. The amount of weight at (D) corresponds to a basic nitrogen content of 10-90, preferably 20-80% by weight of the total nitrogen present.

The proportion of the basic building block (D) can be between 0 and 100% of that from (D).

The solution viscosities of the products according to the invention are in the same order of magnitude as that of the starting polymers, but in general they are a little smaller. The limiting viscosity number of the polymers specified under a) is thus 0.05-1.5 dl / g, preferably 0.05-1.3 dl / g, measured in xylene at 850C.

These limiting viscosity numbers correspond to the number average molecular weight from looo - loo.ooo, preferably looo - 75.ooo, overshoots after the [#] - Mn relationship for high pressure polyethylene.

If the terpolymers described above are used as starting products, the saponification products according to the invention also contain the saponification or transesterification product of the basic building block If the basic building block (C) is in the starting polymer, for example

derived from vinyl acetate, the process products according to the invention can be characterized as follows: (D) (B) (A) (c) 2 PolyCH2-CH1 s CH2-CH1. CH2-CH24. CH2-CH4; z Ns Z (z = OH) CH3 H CH3 CHO The content of basic building block (A) is 5-84, preferably 51-84, that of building block (B) is 0.3-88, preferably 0.4-41, that of building block (D) is 0.2-80, preferably o , 5 - 31, and that of basic building block (C) o> 7 - 14% by weight.

The limiting viscosity number 7 of the polymer specified under c) in the Composition of the preferred range is between 0.05-1.5 dl / g, preferably 0.05-1.3 dl / g, measured in xylene at 850c.

These limiting viscosity numbers correspond to the number average molecular weight from looo - 100,000, preferably looo - 75,000, calculated according to the [#] - Mn relationship for high pressure polyethylene.

Each of these basic building blocks has one or more in the IR spectrum characteristic bands, namely: (A) at 286o and 720 cm-1, (B) at 1660 cm-1, (D) at 3340 cm 1 and (D ') at 2705, 2440, 1600 cm 1; the basic vinyl acetate building block shows bands at 1730 cm-1 and in the region of 1250 + 50 cm-1; after saponification the band at 1730 cm-1 has disappeared.

The copolymers according to the invention are random copolymers in the sense of the copolymerization theory (see L. Kflchler "Polymerisationskimetik", Springer-Verlag, Berlin 1951, p. 160 ff.).

In contrast, block polymers, in which long blocks are the basic building blocks (A), (B), (D), (D ') or optionally (C) are included, unlikely.

The nitrogen contents, which are determined by elemental analysis, are 0.3-22.0, preferably 0.8-10% by weight. The proportion of basic nitrogen is lo - 90, preferably 20 - 80, wt.

the total nitrogen present; it is determined by titration of the Hydrochloride with methanolic sodium hydroxide solution in toluene or by titration of the free base determined with ethanolic hydrochloric acid in toluene.

The polymers according to the invention react in the form of the free base like a secondary amine. So you get for example with mineral acids and organic Acids Salts, depending on the composition of the polymer and the type of acid in Add coarse or finely divided dispersions or solutions to water.

Regarding their physical and mechanical properties the polymeric amines of the invention have essentially the same character as the starting polymers. They are thermoplastic-plastic-like, waxy, plastic or rubber-elastic and brittle-hard substances.

They can be used in the form of the free bases as catalysts for resins, stabilizers and antistatic agents for plastics, their salts as dispersants or emulsifiers and can be used as a thickener.

Example 1: 20 g each of a copolymer, consisting of - (CH2-CH2) - and Basic building blocks (= poly-ethylene-co- (N-vinyl-N-methylformamide) with 18.8% by weight of N-vinyl-N-methylformamide basic building blocks (copolymer no. 4 in Table 1), 40 ml of toluene and 40 ml of 5N ethanolic hydrochloric acid are refluxed for 8, 30, 50 and 100 hours. The reaction products are extracted with a mixture of ethanol / ether (1: 1) until no more hydrochloric acid can be detected. After careful drying, elemental analysis and titration in toluene Chlorine contents of 1.2, 3.4, 4.3 and 4.5 wt. determined with o.ln methanolic sodium hydroxide solution against phenolphthalein; these chlorine contents correspond to conversions to the hydrochloride of N-vinyl-N-methylamine of 15.6, 44, 2, 56, o and 58.5% by weight.

In Fig. 1, the conversion is plotted as a function of time.

Fig. 3 shows the IR spectrum of the starting polymer and Fig. 4 that of the saponification product (reaction time 30 h, degree of saponification 44).

Comparative experiment 1: 20 g each of a polyethylene-co- (N-vinyl-N-methylacetamide) with 16.6% by weight of N-vinyl-N-methylacetamide basic building blocks (Copolymer No. 9 of Tab. 1) are implemented according to example 1.

The reaction products have chlorine contents of <0.3, <0.3, 0.3 and 0.5 wt.%, Which conversions to the hydrochloride of N-vinyl-N-methylamine of <5, <5, 5 and 9.2% by weight correspond. In Fig. 1 is the conversion as a function applied over time.

Example 2S 2o g each of a polyethylene-co- (N-vinyl-N-methylformamide) with 34.2% by weight of N-vinyl-N-methylformamide basic building blocks (copolymer no.5 of Tab. lr are implemented according to example t.

The reaction products have chlorine contents of 5.2, 6.8, 7.3 and 7.7 Weight%, which sales to the hydrochloride of N-vinyl-N-methylamine of 39.0, 51, o, 54.5, 57.2% by weight correspond. In Fig. 2, the conversion is plotted as a function of time.

The IR spectrum of the hydrochloride corresponds qualitatively to that in Fig. 4 spectrum shown; the intensity of the bands at 2705> 2440, 1660 and 1600 cm 1 is increased.

Comparative experiment 2: 20 g each of a polyethylene-co- (N-vinyl-N-methylacetamide) with 31.8% by weight of N-vinyl-N-methylacetamide basic building blocks (copolymer no. lo in Tab. 1) are implemented according to example 1. The reaction products contain chlorine of <0.5, <0.5, 0.5, 1.0% by weight, which conversions to the hydrochloride of N-vinyl-N-methylamine of <4.3, <4.3, 4.3 and 8.6% by weight. In Fig. 2 the conversion is as Plotted as a function of time.

Example 3: 20 g each of a polyethylene-co- (N-vinyl-N-methylformamide) with 18.8% by weight of N-vinyl-N-methylformamide basic building blocks (copolymer no. 4 of Tab. 1), 70 ml of water, lo ml of methanol and 6 ml of concentrated hydrochloric acid are 8, 30, Heated under reflux for 50 and 100 hours. The reaction products are with a mixture Acetone / water (4: 1) extracted until no more free hydrochloric acid can be detected. After reprecipitation from toluene with acetone and drying are elemental analysis and by titration in toluene with o, l n methanolic NaOH chlorine contents of 0.5,, 8, 1.1 and 3.6 wt.

determined; these chlorine contents correspond to conversions to the hydrochloride of the N-vinyl-N-methylamine of 7.3, 12.4, 16, o, 52.3% by weight.

In Fig. 1, the conversion is plotted as a function of time.

Example 4: 20 g each of a polyethylene-co- (N-vinyl-N-methylformamide) with 34.2% by weight of N-vinyl-N-methylformamide basic building blocks (copolymer no.5 of Tab. 1) are reacted according to Example 3 Reaction products have chlorine contents of 1.85, 3.8, 5.3 and 6.9% by weight, which are conversions to the hydrochloride of the N-vinyl-N-methylamine of 13.4, 27.5, 38.4 and 50.0% by weight. In Fig. 1 shows the conversion as a function of time.

The IR spectrum corresponds to that given in Example 2.

Example 5: 2o g of a polyethylene-co- (N-vinyl-N-methylformamide) with 6.7% by weight of N-vinyl-N-methylformamide basic building blocks (copolymer no. 1 in Tab. 1) are implemented according to Example 1 for 50 hours. The reaction product has a chlorine content of 0.7% by weight; a conversion to the hydrochloride corresponds to this chlorine content of the N-vinyl-N-methylamine of 25% by weight. The free base has a nitrogen content of 1.1% by weight. Limiting viscosity number of the free base: [#] = 0.516 (dl / g), in xylene at 85 ° C.

The IR spectrum of the hydrochloride corresponds qualitatively to that in Fig. 4 spectrum shown; the intensity of the bands at 3340, 2705, 2440 and 1600 cm-1 is small.

Elemental analysis of the hydrochloride: C = 83S7%, H = 14.3%, N = 1.1 , C1 = 0.7%.

1 g of the free base consumes 322 meq of acid. Example 6: 20 g of one Polyethylene-co- (N-vinyl-N-methylformamide) with 10.3% by weight of N-vinyl-N-methylformamide (Copolymer No. 2 of Tab. 1), lo ml of concentrated hydrochloric acid and 50 ml of n-butanol are refluxed for 30 hours with stirring. The reaction product is with a mixture of acetone / water (4: 1) extracted until no more free hydrochloric acid can be detected is. After reprecipitation from toluene with acetone and drying, elemental analysis and a chlorine content of 1.95% by weight determined by titration; corresponds to this chlorine content a conversion to the hydrochloride of N-vinyl-N-methylamine of 46% by weight.

The free base has a nitrogen content of 1.7% by weight.

Limiting viscosity number of the free base [#] = 0.60 (dl / s), in xylene at 85 ° C.

The free base is soluble in toluene and xylene when hot.

4 g of the polymer result in 20 ml of water with the addition of an equivalent Amount of acetic acid on boiling an emulsion which, when cooled, is stable while stirring is.

The IR spectrum of the hydrochloride corresponds qualitatively to that in Fig. 4 spectrum shown; the bands at) 540, 2705, 2440 and 1600 cm 1 are from lower intensity.

Elemental analysis of the hydrochloride: C = 81.8%, H = 14.0%, N = 1.6 %, C1 = 1.95%.

1 g of the free base consumes 0.55 meq of acid.

Example 7: 800 g of a polyethylene-co- (N-vinyl-N-methylformamide) with 19.1% by weight of N-vinyl-N-methylformamide (copolymer no. 3 in Table 1), 1500 ml of n-butanol and 300 ml of concentrated hydrochloric acid are refluxed with stirring for 24 hours. To determine the degree of saponification, a sample is worked up in accordance with Example 1; the chlorine content of this sample is determined by elemental analysis and titration to be 5.4 % By weight of chlorine determined, which corresponds to a conversion to the hydrochloride of N-vinyl-N-methylamine of 69% by weight.

After adding 100 ml of concentrated ammonia solution, it is kept under constant Addition of water n-butanol distilled off azeotropically.

The aqueous dispersion obtained is mixed with 5000 ml of water under intensive Stir diluted, made alkaline with 250 ml of concentrated ammonia solution and Stirred for 5 hours. The reaction product is then filtered with water Washed free of chlorine and dried at 80 ° C. The yield is 750 g.

Elemental analysis: C = 81.9%, H = 13.5%, N = 3.2%, C1 = <0.3 %.

1 g of polymer consumes 1.5 meq of acid, i.e. 66% by weight of what is present Nitrogen is in the form of free secondary amino groups.

IR spectrum: characteristic bands at 3340, 2860, 1660, 720 cm-1.

Limiting viscosity number: [#] = 0.18 (dl / g), in xylene at 85 ° C.

Density = 0.918 (g / cm3).

Flow point / dropping point (according to Ubbelohde): 111/118 ° C.

Soluble in heat in benzene, toluene, iso-octane, methylene chloride, Chloroform, n-butanol; insoluble in methanol, ether, acetone, water. With hydrochloric acid, Phosphoric acid, acetic acid, water-soluble salts are obtained.

Limiting viscosity number of the acetate: [#] = 0.24 (dl / g), water at 25 ° C.

Example 8: 20 g of a polyethylene-co- (N-vinyl-N-methylformamide) with 72.5% by weight of N-vinyl-N-methylformamide basic building blocks (copolymer no. 6 of Tab. 1), 6o ml of i-propanol and 15 ml of concentrated hydrochloric acid are stirred for 30 hours heated to reflux. The reaction product is precipitated with acetone, dried, in Dissolved water, freed from excess hydrochloric acid by dialysis and freeze-dried. The product purified in this way has a chlorine content of 16.2% by weight, which corresponds to one Conversion to the hydrochloride of N-vinyl-N-methylamine of 58% by weight. The free base possesses a nitrogen content of 13.9% by weight.

Limiting viscosity number of the hydrochloride: £ = 0.230 (dl / g), water at 250C.

The IR spectrum of the hydrochloride corresponds qualitatively to that in Fig. 4 spectrum shown. However, the bands at 3340, 2705, 2440 and 1600 com 1 are of high intensity; the bands at 286o and 720 appear only with less Intensity.

Elemental analysis of the hydrochloride: C = 56%, H = 10.2%> N = 11.7 %> Cl = 16.2%.

1 g of the free base consumes 5.4 meq of acid.

Example 9: 20 g of a polyethylene-co- (N-vinyl-N-methylformamide) with 95% by weight of N-vinyl-N-methylformamide basic building blocks (copolymer no. 7 of Tab. 1), 30 ml of concentrated hydrochloric acid and 50 ml of water are refluxed for 30 hours heated. The reaction product is rolled with acetone, dried, dissolved in water, thereby dialysis of Excess hydrochloric acid freed and freeze-dried.

The product purified in this way has a chlorine content of 26.8% by weight corresponds to a conversion to the hydrochloride of N-vinyl-N-methylamine of 74% by weight. The free base has a nitrogen content of 20.3% by weight.

Limiting viscosity number of the hydrochloride: [#] = 0.220 (dl / g), water at 250C.

The IR spectrum of the hydrochloride shows, among other things, high intensities Bands at 3340, 2705, 2440 and 1600 cm-1.

Elemental analysis of the hydrochloride: C = 45.0%, H = 9.3%, N = 14, o %, Cl = 26.8%.

1 g of the free base consumes 10.4 meq of acid.

Example lo: loo g of a polyethylene-co-vinyl acetate-co (N-vinyl-N-methyl form amide) with 4% by weight vinyl acetate building blocks and 14% by weight N-vinyl-N-methylformamide building blocks (Copolymer No. 8 of Table 1), 250 ml of n-butanol and 50 ml of concentrated hydrochloric acid are refluxed for 30 hours with stirring. The procedure is as follows in Example 8. The reaction product contains 3.0% by weight of chlorine, which corresponds to one Conversion to the hydrochloride of N-vinyl-N-methylamine of 57% by weight.

Limiting viscosity number of the free base: [#] = 0.240 (dl / g), xylene at 85 ° C.

The IR spectrum of the hydrochloride corresponds qualitatively to that in Fig. 4 spectrum shown. Characteristic is the disappearance of the in the spectrum the carbonyl band present in the starting substance at 1730 cm-1; it proves the saponification the basic vinyl acetate building block to the basic vinyl alcohol building block.

Elemental analysis of the hydrochloride: C = 79.9%, H = 13.5%, N = 2.3 %, C1 G 3.0%.

1 g of the free base consumes 0.9 mVal of acid.

Claims (13)

P a t e n t a n s p r ii c h e 1. Copolymers, consisting of the randomly arranged basic building blocks - (CH2-CH2) - (A), the content of (A) being 5-99% by weight, that of (B) 0.2-88% by weight and that of (D) 0.13-88% by weight. 2. Copolymers according to claim 1, characterized in that they 52 - Contain 96% by weight (A), 1-41.5% by weight (B) and 0.7-31% by weight (D). 3. Copolymers, consisting of the randomly arranged basic building blocks - (CH2-CH2) - (A), (C), where the content of (A) 51-84% by weight, that of (z = OH) (B) 0.4-41% by weight, that of (D) 0.5-31% by weight and that of (C) 0.7-14% by weight. 4. Copolymers according to Claims 1-3, characterized in that the number average molecular weight is between looo and loo, ooo. 5. Copolymers according to Claims 1 and 3, characterized in that the basic building block (D) is entirely or partially through the basic building block is replaced, where X # denotes the anion of an acid. 6. Copolymers according to claim 5, characterized in that X is a hydrogen halide, a Means sulfate, phosphate or acetate radical. 7. Copolymers according to claim 1, produced by solvolysis of copolymers consisting of the randomly arranged basic building blocks -pCH2-CH2- # (A) and and subsequent treatment of the solvolysis products with alkali, ammonia or anion exchangers. 8. Copolymers according to claim 3, produced by solvolysis of copolymers, consisting of the randomly arranged basic building blocks - (CH2-CH2) - (A), where Z = C1, -COOR ', -OR', -OCOR 'and R = H or -CH3 and R' = CH3 or C2H5, and subsequent treatment of the solvolysis products with alkali, ammonia or anion exchangers. 9. Copolymers according to claim 5, produced by acidic solvolysis of copolymers which, in a random arrangement, consist of 5-98% by weight of the basic building block - (CH2-CH2) - (A) and 95-2% by weight of the basic building block exist. lo. Process for the preparation of basic and cationic copolymers by solvolysis of copolymers at elevated temperature, characterized in that the saponification is carried out on copolymers which are composed of the randomly arranged basic building blocks - (CH2-CH2) - (A), and if necessary (C) consist, where Z = C1, -COOR ', -OR', -OCOR 'and R = H or -CH3 and R' = -CH3 or C2H5. 11. The method according to claim 10, characterized in that the starting polymer consists of 5 - 98% by weight (A) and 95 - 2% by weight (B). 12. The method according to claim Be, characterized in that the starting polymer consists of 4-78% by weight (A), 95-2% by weight (B) and 1-20% by weight (C). 13. The method according to claimless, characterized in that the limiting viscosity number [#] of the starting polymers in xylene at 850C or methylene chloride or water 250C is 0.05 to 1.5 (dl / g), starting polymers with less than 50% by weight of (B) in xylene, starting polymers with 50 - 80 wt. of (B) in methylene chloride, and starting polymers with more than 80% by weight can be measured on (B) in water. L e r s e i t e