CA2213009A1

CA2213009A1 - Copolymers of unsaturated dicarboxylic acids or their anhydrides and vinyl-terminated oligo-olefines and their reaction products with nucleophilic agents

Info

Publication number: CA2213009A1
Application number: CA002213009A
Authority: CA
Inventors: Dieter Faul; Joachim Rosch; Hans Peter Rath; Wolfgang Gunther; Knut Oppenlander; Helmut Mach
Original assignee: Individual
Current assignee: BASF SE
Priority date: 1995-03-13
Filing date: 1996-03-01
Publication date: 1996-09-19
Also published as: DE59603861D1; JPH11502239A; WO1996028486A1; DE19508656A1; KR100348957B1; KR19980702903A; EP0815150B1; AU5100896A; MX9706775A; EP0815150A1

Abstract

Copolymers I which carry functional groups consist of (a) from 30 to 70 mol% of at least one monoethylenically unsaturated C4-C12-dicarboxylic acid or the anhydride thereof and (b) from 30 to 70 mol% of at least one oligomer of a l-olefin of 3 to 14 carbon atoms, at least 85% of which is present as an isomer having a terminal vinyl group of the formula -CH=CH2 and which has an average molecular weight of from 300 to 10, 000.

Reaction products of the copolymers I with compounds containing NH, OH or SH functional groups are suitable as dispersants for detergent and cleaning agent formulations, water repellents for leather and skins, flow improvers and paraffin dispersants for crude oils and refined mineral oil fractions and lubricant and fuel additives.

Description

~ BASF Aktiengesellschaft 950193 O.Z. 0050/45722 Copolymers of unsaturated dicarboxylic acids or anhydrides thereof and vinyl-terminated oligoolefins and reaction products thereof with nucleophilic agents The present invention relates to novel copolymers which carry functional groups and are obtained from unsaturated dicarboxylic acids or anhydrides thereof and vinyl-terminated oligoolefins, a process for the preparation of these copolymers and reaction 10 products thereof with nucleophilic agents. The present invention furthermore relates to various uses of such reaction products.

The published German Patent Application P 43 30 971.2 (1) discloses terpolymers which contain functional groups and are 15 obtained from - 20-60 mol% of monoethylenically unsaturated C4-C6-dicarboxylic acids or anhydrides thereof, 20 - 10-70 mol% of oligomers of propene or of branched l-olefins of 4 to 10 carbon atoms having an average molecular weight of from 300 to 5000 and - 1-50 mol% of copolymerizable monoethylenically unsaturated compounds.

oil-soluble reaction products of these terpolymers with amines are suitable as fuel additives and lubricant additives.

30 W0-A 90/03359 (2) describes polymers which can be used as additives in lubricating oils and in some cases have dispersant properties for sludge and solid particles contained therein. Some of these polymers are also viscosity index improvers, ie. they ensure that, when the temperature increases, the viscosity of 35 lubricating oil decreases to a substantially lesser extent than in a lubricating oil without such an additive.

The polymers disclosed in (2) are composed of maleic acid or fumaric acid or derivatives thereof and an olefin whose molecular 40 weight is sufficiently high for the polymer prepared from these monomers to be oil-soluble, and are reacted with amines. This olefin must carry at least 20% of alkylvinylidene groups.

The polymers disclosed in publication (2) do not have 45 satisfactory properties for all applications, in particular the viscosity/temperature behavior of lubricating oils which contain these polymers as additives is still unsatisfactory in many CA 02213009 1997-09-0~

BASF Aktiengesellschaft 950193 O.Z. 0050/45722 cases. Furthermore, the dispersant action of these compounds in industrial use is not satisfactory in all cases.

It is an object of the present invention to provide lubricating 5 oil additives which no longer have the disadvantages of the prior art.

We have found that this object is achieved by copolymers I which carry functional groups and consist of:
(a) from 30 to 70 mol% of at least one monoethylenically unsaturated C4-Cl2-dicarboxylic acid or the anhydride thereof and 15 (b) from 30 to 70 mol% of at least one oligomer of a 1-olefin of 3 to 14 carbon atoms, at least 85% of which is present as an isomer having a terminal vinyl group of the formula -CH=CH2 and which has an average molecular weight of from 300 to 10, 000.
The novel copolymers I contain no further comonomers apart from (a) and (b).
The novel copolymers I are used as intermediates for the 25 preparation of a very wide range of industrial compositions having in some cases outstanding performance characteristics, as described below.

Preferred monomers (a) are monoethylenically unsaturated 30 C4-C6-dicarboxylic acids or anhydrides thereof, eg. maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride and methylenemalonic anhydride and mixtures thereof with one another. Maleic anhydride is preferred.
Suitable monomers (b) are oligomers of propene or of a linear 1-olefin of 4 to 14 carbon atoms. These oligomers are as a rule composed of at least 3 olefin molecules. They contain at least 85%, in particular at least 90%, of vinyl-terminated isomer.
40 Vinyl-terminated oligoolefins are more reactive than the corresponding vinylidene-terminated macromers. In the free radical copolymerization, it is therefore possible to achieve higher degrees of polymerization and consequently higher molecular weights, which has an advantageous effect on the 45 performance characteristics of the end products. Their average molecular weight is from 300 to 10,000, in particular from 500 to 5000. Examples are oligomers of propene, of n-butene, of CA 02213009 1997-09-0~

' BASF Aktiengesellschaft 950193 0.Z. 0050/45722 .

n-pentene, of n-hexene and of n-decene, at least 85% of the copolymerizable terminal groups of the oligomer being present in the form of a vinyl group. Oligopropenes and oligopropene mixtures of 9 to 400, in particular of 12 to 300, carbon atoms 5 are preferred. Such vinyl-terminated oligoolefins are obtainable, for example, according to EP-A 268 214 (Example 2), by means of a metallocene catalyst of the bis-pentamethylcyclopentadienyl-zirconium dichloride type.

10 The copolymers I contain the monomers (a) in amounts of from 30 to 70, preferably from 40 to 60, mol% and the monomers (b) in amounts of from 30 to 70, preferably from 40 to 60, mol%.

Copolymers I which carry functional groups and in which the 15 component (a) is maleic anhydride and the component (b) is an oligopropene or an oligopropene mixture, each of 9 to 400 carbon atoms, are particularly preferred.

The present invention also relates to a process for the 20 preparation of copolymers I which carry functional groups, which comprises subjecting (a) from 30 to 70 mol% of at least one monoethylenically unsaturated C4-C12-dicarboxylic acid or the anhydride thereof to free radical polymerization with (b) from 30 to 70 mol% of at least one oligomer of a 1-olefin of 3 to 14 carbon atoms, at least 85% of which is present as an isomer having a terminal vinyl group of the formula -CH=CH2 and which has an average molecular weight of from 300 to 10, 000.

The copolymers I can be prepared by all known conventional polymerization methods, for example by mass, emulsion, 35 suspension, precipitation and solution polymerization. All stated polymerization processes are usually carried out in the absence of oxygen, preferably in a nitrogen stream.

The conventional apparatuses, for example autoclaves and kettles, 40 are used for all polymerization methods. The mass polymerization of the monomers (a) and (b) is particularly preferred. It can be carried out at from 60 to 300 C, preferably from 80 to 200 C, the lowest polymerization temperature to be chosen preferably being about 20 C above the glass transition temperature of the polymer 45 formed. The polymerization conditions are chosen according to the desired molecular weight of the copolymers. Polymerizations at high temperatures usually give copolymers having low molecular ' BASF Aktiengesellsc~aft 950193 O.Z. 0050/45722 .

weights, whereas polymers having higher molecular weights are usually formed at lower polymerization temperatures.

The copolymerization is preferably carried out in the presence of 5 compounds which form free radicals. Up to 10, preferably 0.2 to 5, % by weight, based on the monomers used in the copolymerization, of these compounds are required. Examples of suitable polymerization initiators are peroxide compounds, such as tert-butyl perpivalate, tert-butyl perneodecanoate, tert-butyl 10 perethylhexanoate, tert-butyl perisobutyrate, di-tert-butyl peroxide, di-tert-amyl peroxide, diacetyl peroxodicarbonate and dicyclohexyl peroxodicarbonate, and azo compounds, eg.
2,2'-azobisisobutyronitrile. These initiators may be used alone or as a mixture with one another. In the mass polymerization, 15 they are preferably introduced separately or in the form of a solution into the polymerization reactor. The monomers (a) and (b) can be copolymerized at above 200 C also in the absence of polymerization initiators.

20 In order to prepare low molecular weight polymers, it is often advantageous to carry out the copolymerization in the presence of regulators. Conventional regulators, such as C1-C4-aldehydes, formic acid or organic SH-containing compounds, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, 25 tert-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan or tert-dodecyl mercaptan, may be used for this purpose. The polymerization regulators are generally used in amounts of from 0.1 to 10% by weight, based on the monomers.

30 In order to prepare higher molecular weight copolymers, it is often advantageous to carry out the polymerization in the presence of chain extenders. Such chain extenders are compounds having diethylenically or polyethylenically unsaturated groups, such as divinylbenzene, pentaerythrityl triallyl ether or esters 35 of glycols, such as glycol diacrylate, glyceryl triacrylate or polyethylene glycol diacrylates. They may be added in the polymerization in amounts of up to 5% by weight.

The copolymerization can be carried out continuously or 40 batchwise. The molecular weight of the copolymers I are as a rule from 1000 to 100,000, in particular from 5000 to 50,000.

The copolymers I can be reacted with nucleophilic agents, ie.
with compounds cont~in;ng NH, OH or SH functional groups, and can 45 thus be derivatized for various fields of use. Accordingly, the present invention also relates to such reaction products II.

CA 02213009 1997-09-0~

BASF Aktiengesellschaft 950193 O.Z. 0050/4572Z

.

Thus, the reaction of the copolymers I with an aqueous alkali metal or alkaline earth metal hydroxide, for example with aqueous potassium or sodium hydroxide solution, gives stable aqueous dispersions (reaction products IIa) which are suitable as 5 dispersants for detergent and cleaning agent formulations and as water repellents for leather and skin. The present invention also relates to aqueous detergent and cleaning agent formulations which contain the reaction products IIa as dispersants in conventional amounts.
The reaction of the copolymers I with saturated or unsaturated aliphatic alcohols of 8 to 30, in particular 10 to 22, carbon atoms, ie. fatty alcohols, such as stearyl alcohol or behenyl alcohol, gives oil-soluble reaction products IIb, which are 15 suitable as flow improvers and paraffin dispersants for crude oils and refined mineral oil fractions. The present invention also relates to crude oils and refined mineral oil fractions which contain the oil-soluble reaction products IIb as flow improvers and paraffin dispersants in conventional amounts.
The reaction of the copolymers I with primary, secondary or tertiary mono- or polyamines or mixtures thereof which carry at least one C6-C30-alkyl, in particular C8-C22-alkyl, or alkenyl radical, ie. fatty amines, such as tridecylamine, gives reaction 25 products IIc which are suitable as corrosion inhibitors for metal substrates.

The reaction of the copolymers I with amines of the formula NHR1R2, where R1 and R2 may be identical or different and may each 30 be hydrogen, an aliphatic or aromatic hydrocarbon radical, a primary or secondary, aromatic or aliphatic aminoalkylene radical, a polyaminoalkylene radical, hydroxyalkylene radical or a polyoxyalkylene radical, which may carry terminal amino groups, or may each be a hetaryl or heterocyclyl radical which may carry 35 terminal amino groups, or, together with the nitrogen atom to which they are bonded, form a ring in which further heteroatoms may also be present, gives reaction products IId which are suitable as additives for lubricants and fuels.

40 Examples of suitable amine components HNRlR2 are:

- ammonia;
- aliphatic and aromatic, primary and secondary amines of 1 to 50 carbon atoms, such as methylamine, ethylamine, propylamine, di-n-butylamine or cyclohexylamine;

CA 02213009 1997-09-0~

~ BASF AXtiengesellschaft 950193 u.~. uu~u/ ~

.
~ 6 - amines in which Rl and R2, together with the nitrogen atom to which they are bonded, form a common ring which may also contain further heteroatoms, such as morpholine, pyridine, piperidine, pyrrole, pyrimidine, pyrroline, pyrrolidine, S pyrazine or pyridazine;
- amines which carry hydroxyalkylene and polyoxyalkylene radicals and in which Rl and/or R2 are a radical --E R3 O ~ H III

where R3 is a C2-C10-alkylene and m is an integer from 1 to 30, such as ethanolamine, 2-aminopropan-1-ol or neopentanolamine;
- polyoxyalkyleneamines which carry terminal amino groups and in which Rl and/or R2 are a radical - R4 o ~ R3 - ~ 3 R5 NR6R7 IV
m where R3~ R4 and R5 are each C2-C10-alkylene, m has the abovementioned meanings and R6 and R7 are each hydrogen, unsubstituted or hydroxyl- or amino-substituted C1-C10-alkyl or C6-C10-aryl, such as polyoxypropylenediamines or bis(3-aminopropyl)tetrahydrofurans.
However, preferred amine components are polyamines in which and/or R2 are a radical of the formula V

~ n 40 where R3, R6 and R7 have the abovementioned meanings and n is an integer from 1 to 6. Particularly suitable polyamines are ethylenediamine, propylenediamine, dimethylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, 45 ethylaminoethylamine, dimethylaminoethylamine, isopropylamino-propylamine, ethylenedipropylenetetramine, 2-diisopropylaminoethylamine, aminoethylethanolamine, CA 02213009 1997-09-0~

BASF Aktiengesellschaft 950193 O.Z. 0050/457ZZ

ethylenepropylenetriamine, N,N,N',N'-tetra(3-aminopropyl)ethylenediamine, 2-(3-aminopropyl)cyclohexylamine, 2,5-dimethylhexane-2,5-diamine and N,N,N',N'',N''-penta-(3-aminopropyl)dipropylenetriamine.
5 Other preferred polyamines are those which contain a heterocyclic structure as a structural component, eg. aminoethylpiperazine.

Mixtures of different amines may also be used as the amine component.
The novel reaction products IId are obtained in a manner known per se, by reacting copolymers I with the stated amines. The molar ratio of the components depends on the number of acid or anhydride groups in the copolymer I. This can be determined in a 15 known manner, for example by titration with a strong base. In general, from 0.1 to 3 equivalents of acid or anhydride groups in the polymer are used per mol of amine. As a rule, the starting materials are mixed for the reaction and are heated to 30-200 C.
The reaction is preferably carried out under an inert gas 20 atmosphere. The reaction can be effected in the presence or absence of solvents. Examples of inert solvents are aliphatic and aromatic hydrocarbons, such as toluene and xylene, as well as mineral oils. The progress of the reaction can be monitored by IR
spectroscopy.
The present application also relates to lubricants and fuels which contain the oil-soluble reaction products IId in the amounts stated below.

30 The lubricants are additive-containing synthetic, semisynthetic and mineral oils, preferably those which are used as engine oils.
The synthetic oils comprise synthetic esters and polymers of ~-olefins. The reaction products IId are added to the lubricants in general as a concentrate in an inert solvent, such as a 35 mineral oil. These concentrates may contain further conventional additives, such as corrosion inhibitors, antiabrasion agents, detergents, antioxidants and pour point improvers.

The reaction products IId are added to the lubricants in amounts 40 of from 1 to 15, preferably from 0.5 to 10, % by weight.

In fuels, such as gasoline or diesel fuel, the reaction products IId are used as detergents for keeping the intake system clean.
Owing to their dispersant properties, they also have an 45 advantageous effect on engine lubricants, which they may enter during operation of the engine. From 20 to 5000 ppm, preferably CA 02213009 1997-09-0~

BASF Aktiengesellschaft 950193 0.Z. 0050/45722 from 50 to 1000 ppm, based on the fuel, are added for this purpose.

The novel oil-soluble reaction products IId generally have 5 excellent viscosity/temperature behavior in virtually all lubricants. They also exhibit an excellent dispersant effect in virtually all cases. The superior performance characteristics of the reaction products IId are illustrated in the Examples below.

lO Example 1. Preparation of the vinyl-terminated oligopropenes (b) General preparation method:
30 ml of a 1.5 molar solution of methylalumoxane in toluene were initially taken in a stirred 2 l autoclave, and 900 ml (13.3 mol) of a liquid propene were condensed and heated to the temperature stated in Table 1. The resulting pressure was 20 bar. Thereafter, 20 64.3 mg (0.17 mmol) of bis-pentamethylcyclopentadienylzirconium dichloride, dissolved in 7 ml of a 1.5 molar solution of methylalumoxane in toluene, were added and oligomerization was carried out for the time stated in Table 1. The aluminum/
zirconium atomic ratio was 250:1. A yield of 590 ml of oligomer 25 mixture was obtained. The average molecular weights were determined by means of gel permeation chromatography and using polystyrene standards having a narrow molecular weight distribution.

30 Table 1: Data for the oligopropenes (b) used Oligo- Oligomerization Oligomerization Average Vinyl propene temperature [~C] time [min] molecular content weight [%]
bl 50 60 750 92 b2 35 120 900 93 b3 20 180 1400 93 2. Preparation of the copolymers I

Example 2.1 45 200 g of the oligomer bl were heated to 100 C in a gentle stream of nitrogen in a reactor, and 32.7 g of maleic anhydride (in liquid form as a melt at about 75 C) were metered in over 4 hours.

CA 02213009 1997-09-0~

BASF Aktiengesellschaft 950193 O.Z. 0050/45722 At the same time, a solution of 3.5 g of tert-butyl peroctoate, dissolved in 10 g of toluene, was metered in over 4 hours.
Thereafter, the mixture was heated to 150 C and a solution of 2.3 g of di-tert-butyl peroxide in 10 g of toluene was metered in 5 over 1 hour and, after the end of the reaction, polymerization was continued for a further 0.5 hour at this temperature. The copolymer thus obtained had a molecular weight of 12,000.

Example 2.2 95 g of the oligomer b2 were heated to 150 C in a gentle stream of nitrogen in a reactor, and 10.3 g of maleic anhydride (in liquid form as a melt at about 75 C) were metered in over 4 hours. At the same time, a solution of 2.1 g of di-tert-butyl peroxide, 15 dissolved in 5 g of toluene, was metered in over 4.5 hours.
Polymerization was then continued for a further hour at this temperature. The copolymer thus obtained had a molecular weight of 48,000.

20 Example 2.3 201.5 g of the oligomer b3 were heated to 150 C in a gentle stream of nitrogen in a reactor, and 7.3 g of maleic anhydride tin liquid form as a melt at about 75 C) were metered in over 4 hours.
25 At the same time, a solution of 3.1 g of di-tert-butyl peroxide, dissolved in 10 g of toluene, was metered in over 4.5 hours.
Polymerization was then continued for a further hour at this temperature. The copolymer thus obtained had a molecular weight of 15,600.
The molecular weights of the copolymers from Examples 2.1, 2.2 and 2.3 were determined with the aid of high pressure gel permeation chromatography. The eluent used was tetrahydrofuran.
Calibration was effected with polystyrene fractions having a 35 narrow molecular weight distribution.

3. Preparation of the oil-soluble reaction products IId General preparation method:
A copolymer according to Examples 2.1 to 2.3 in xylene was initially taken at 70 C, an amine or polyamine was added and refluxing was carried out until the expected amount of water of reaction had separated off. After removal of the solvent, the 45 product was obtained in the form of a pale yellow to amber, viscous residue. The IR absorption bands of the products were at CA 02213009 1997-09-0~

BASF AXtiengesellschaft 950193 O.Z. OU5U/457zz about 1770 and about 1700 cm-l. The reactions carried out are shown in Table 2 below:

Table 2 Example Polymer Amine component Molar ratio according to anhydride/amine example lO 3.1 2.1 Triethylenetetramine 1:1 3.2 2.1 Triethylenetetramine 1.85:1 -3.3 2.1 N-Aminoethylpiperazine 1.5:1 3.4 2.1 N-Aminoethylpiperazine 2:1 3.5 2.2 Triethylenetetramine 1:1 3.6 2.2 N-Aminoethylpiperazine 1.5:1 3.7 2.2 Polyoxypropylenediamine 2:1 (molecular weight about 400) 3.8 2.3 Triethylenetetramine 1:1 3.9 2.3 Triethylenetetramine 2:1 25 4. Preparation of the comparative products Comparative additive Vl Reaction product of the copolymer according to Example 6 of 30 WO-A-90/03359 (2) and triethylenetetramine The stated starting materials were reacted similarly to the above Examples 3, in a molar ratio of 1:1.

Comparative additive V2 Reaction product of the copolymer according to Example 6 of (2) and triethylenetetramine 40 The stated starting materials were reacted similarly to the above Examples 3, in a molar ratio of 2:1.

5. Testing of the viscosity/temperature behavior 45 The additives were tested in a concentration of 6% by weight in a 5W-30 engine oil. The results are listed in Table 3.

CA 02213009 1997-09-0~

BASF Aktiengesellschaft 950193 O.Z. 0050/45722 -Table 3 Additive Viscosity at Viscosity at -25 C Solubility according to 100 C [mm2s~l] [mPas] CCS
Exampleaccording to Ubbelohde no additive 7.55 1900 3.1 10.89 2950 clear solution 3.2 10.23 3100 clear solution 3.5 13.33 3200 slightly cloudy solution 3.8 12.42 3300 clear solution 3.9 14.40 3400 clear solution Vl 9.00 3100 cloudy solution V2 9.19 3200 cloudy solution 25 The novel additives ~3.1, 3.2, 3.5, 3.8 and 3.9) are clearly superior to those of the prior art (Vl and V2) owing to their greater viscosity-enhancing effect at high t~mrerature. The low-temperature viscosity of the oils to which additives had been added according to the invention is in the range of the prior 30 art.

6. Testing of the dispersant effect The dispersant effect was tested by means of a ~pot test as 35 described in Les Huiles pour Moteurs et la Graissage des Moteurs, A.Schilling, Vol. 1, page 89 et seq., 1962. For this purpose, 3%
strength by weight mixtures of the additives in a diesel oil were prepared. The dispersions thus obtained were developed on a filter paper in the same way as a chromatogram. The evaluation 40 scale extended from 0 to 1000: the higher the value obtained, the better the dispersant effect of the additive. The results are listed in Table 4.

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Table 4 Additive 10 min at 10 min at RT 10 min at 10 min at according to RT without 1% of water 250 C 250 C with 5 Example water without water water 3.2 651 624 658 638 3.5 671 670 652 676 10 3.8 659 675 688 671 3.9 679 694 706 718 RT= room temperature The novel additives (3.2, 3.5, 3.8 and 3.9) have a significantly better dispersant effect than the prior art additives (V1 and V2) 20 in virtually all cases.

Claims

claims

1. A copolymer I which carries functional groups and consists of (a) from 30 to 70 mol% of at least one monoethylenically unsaturated C4-C12-dicarboxylic acid or the anhydride thereof and (b) from 30 to 70 mol% of at least one oligomer of a 1-olefin of 3 to 14 carbon atoms, at least 85% of which is present as an isomer having a terminal vinyl group of the formula -CH=CH2, which has an average molecular weight of from 300 to 10,000 and is composed of at least 3 olefin molecules.

2. A copolymer I which carries functional groups as claimed in claim 1, in which the component (a) is maleic anhydride and the component (b) is an oligopropene or an oligopropene mixture, each of 9 to 400 carbon atoms.

3. A process for the preparation of a copolymer I which carries functional groups, as claimed in claim 1 or 2, which comprises subjecting (a) from 30 to 70 mol% of at least one monoethylenically unsaturated C4-C12-dicarboxylic acid or the anhydride thereof to free radical polymerization with (b) from 30 to 70 mol% of at least one oligomer of a l-olefin of 3 to 14 carbon atoms, at least 85% of which is present as an isomer having a terminal vinyl group of the formula -CH=CH2, which has an average molecular weight of from 300 to 10,000 and is composed of at least 3 olefin molecules.

4. A reaction product II of a copolymer I as claimed in claim 1 or 2 with compounds containing NH, OH or SH functional groups.

5. A reaction product IIa of a copolymer I as claimed in claim 1 or 2 with an aqueous alkali metal or alkaline earth metal hydroxide.

6. Use of a reaction product IIa as claimed in claim 5 in the form of an aqueous dispersion as a dispersant for detergent and cleaning agent formulations.

7. An aqueous detergent or cleaning agent formulation, containing a reaction product IIa as claimed in claim 5 as a dispersant in a conventional amount.

8. Use of a reaction product IIa as claimed in claim 5 in the form of an aqueous dispersion as a water repellent for leather and skins.

9. An oil-soluble reaction product IIb of a copolymer I as claimed in claim 1 or 2 with a saturated or unsaturated aliphatic alcohol of 8 to 30 carbon atoms.

10. Use of an oil-soluble reaction product IIb as claimed in claim 9 as a flow improver or paraffin dispersant for crude oils and refined mineral oil fractions.

11. A crude oil or a refined mineral oil fraction, containing an oil-soluble reaction product IIb as claimed in claim 9 as a flow improver or paraffin dispersant in a conventional amount.

12. A reaction product IIc of a copolymer I as claimed in claim 1 or 2 with a primary, secondary or tertiary mono- or polyamine which carries at least one C6-C30-alkyl or C6-C30-alkylene radical.

13. Use of a reaction product IIc as claimed in claim 12 as a corrosion inhibitor for metal substrates.

14. An oil-soluble reaction product IId of a copolymer I as claimed in claim 1 or 2 with an amine of the formula HNR1R2, where R1 and R2 may be identical or different and may each be hydrogen, an aliphatic or aromatic hydrocarbon radical, a primary or secondary, aromatic or aliphatic aminoalkylene radical, a polyaminoalkylene radical, a hydroxyalkylene radical or a polyoxyalkylene radical, which may carry terminal amino groups, or may each be a hetaryl or heterocyclyl radical which may carry terminal amino groups, or, together with the nitrogen atom to which they are bonded, form a ring in which further hetero atoms may also be present.

15. Use of an oil-soluble reaction product IId as claimed in claim 14 as an additive for lubricants and fuels.

16. A lubricant containing from 1 to 15% by weight of an oil-soluble reaction product IId as claimed in claim 14.

17. A fuel containing from 20 to 5000 ppm of an oil-soluble reaction product IId as claimed in claim 14.