DE10148284A1 - Process for the production of raffinates and extracts of polymers - Google Patents

Abstract

The invention relates to a method for producing raffinates and extracts of polymers having an M<SB>N</SB> that ranges from 500 to 5000 Dalton like those resulting during the polymerization of alkenes with, in essence, four carbon atoms, whereby the polymers and extracts are predominately comprised of monoalkenes. The raffinates and extracts are produced by: a) treating the polymer with a solvent that is insoluble or slightly soluble therein with an E<SB>T</SB>(30) value ranging from 38 to 57 kcal/mol or with a mixture consisting of two or more solvents of this type, and by; b) separating the resulting raffinate phase and extract phase from one another and optionally liberating them from the solvent. The invention also relates to the novel raffinates and extracts obtained in this manner, to certain derivatives of these products and to the use of these raffinates, extracts and derivatives as auxiliary agents in fuels and lubricating oils. The invention additionally relates to the fuels and lubricating oils of this type.

Description

The present invention relates to a process for the production of raffinates and extracts of such polymers with M _N of 500 to 5000 Daltons, as they arise in the cationic polymerization of alkenes with essentially four carbon atoms, the polymers and extracts consisting predominantly of monoalkenes.

The invention further relates to new raffinates and extracts which the products of this process are certain derivatives of these Products as well as the use of these raffinates, extracts and Derivatives as auxiliary substances in fuels and lubricants. Farther The invention relates to such fuels and lubricants.

Low molecular weight polymers of isobutene and isobutene / butene mixtures with number average M _N of 500 to 5000 daltons, hereinafter referred to as "polymers", are important precursors for dispersants which are used in lubricants or in fuels. The polymers are produced industrially practically exclusively by (alkyl) aluminum chloride or boron trifluoride-catalyzed cationic polymerization of suitable alkene streams or technical alkene / alkane mixtures such as raffinate I or FCC. Other, albeit less common, catalysts are titanium tetrachloride and boron trichloride. Naturally, this polymerization always produces a mixture of alkenes of different chain lengths and, within a group of molecules of the same chain length, different degrees of branching, different positions and, if appropriate, different numbers of double bonds. By choosing suitable reactants, different classes of dispersants can be obtained from such polymers: With an electron-deficient double bond, such as that present in maleic anhydride, terminal double bonds in the polymer react in a thermal ene reaction to form an adduct with a comparatively polar anhydride end group. In this way, the corresponding polyisobutenylsuccinic anhydride ("PIBSA") is obtained from a specific polyisobutene and maleic anhydride, and from this the reaction with polyamines gives the imide "PIBSI", which is generally classified as an ashless dispersant.

Another class of derivatives of the polymers are theirs Oxo derivatives, which are obtained by hydroformylation of the double bonds and subsequent hydrogenation of the intermediate aldehydes are available. For such products based on polyisobutene often used the collective name "PIB-oxo".

Accordingly, "PIBA" means those products which by amination of the oxo products or of epoxides Polyisobutens are available.

As further derivatives of the polymers, which in Special applications are also used Derivatization of the double bonds accessible halides, acids, Anhydrides, esters, alkylphenols (mainly to 4-alkylphenols) and to name Mannich bases of the alkylphenols.

The polymers can generally be adequately characterized by their molar mass distribution, expressed by the weight average M _W , the number average M _N or their quotient M _W / M _N (dispersity, D), the degree of branching in the hydrocarbon chain, the proportion of molecules with terminal ends Double bonds, especially their viscosity and further by the combination of two or more of these sizes.

Are the polymers beyond heteroatoms or Derivatized heteroatom-containing groups, this gives them Derivatization of the polymers is usually also a characteristic polarity.

Based on the comparatively easily measurable viscosity as well as the polarity and the sizes M _N , M _W and D, the person skilled in the art can in most cases already decide which polymer or which of the derivatives derived from a polymer best meets the requirements of a particular intended use.

If, for example, ash-free dispersants for the lubricant sector based on polyisobutene are to be made available by thermal ene reaction, a high proportion of terminal double bonds in the polyisobutene used is advantageous because the ene reaction then proceeds with increased yield. In order to assess whether the addition products obtained in this way are suitable for a specific purpose, their M _N , viscosity and polarity can also be used.

Motor oils are lubricants that affect the effect of such dispersants can be illustrated: an important task The engine oils can be seen in the entire area of the Engine operating temperature the friction between engine parts, which move against each other, minimize and thereby permanent and more even engine performance contribute. Ideally, the engine oils already form part of this Starting the engine quickly apply an oil protection film to the moving Share which over the entire service life even in small Districts of the surface so wetted should not tear off.

Another effect of such engine oils is that they small solid particles in the engine, which are the finest metal abrasion or solid and / or liquid insoluble residues of the power and Lubricant combustion can prevent buildup to form in the engine, which subsequently causes further abrasion damage can pull themselves. Ashless dispersants, ash-forming Dispersants, pour point depressants, zinc dithiophosphate, Antioxidants and viscosity modifiers are common additives for Motor oils, which are the base oils in more or less large quantities be added.

The dispersant additive usually causes the insoluble ones Residues are dispersed or their aggregation is prevented. The viscosity of such oils is determined by the dispersant usually only moderately increased. One of the main tasks of the Dispersants therefore consists of natural and synthetic Base oils or their mixtures to permanently improve To help lubricating properties in the sense explained above. One is practical in the area of low engine temperature aiming for the lowest possible viscosity of the engine oil.

Even this simple consideration makes it clear that the ultimately the lubricating effect is the result of a complicated interaction of the "base oils" used, the dispersant and other additives used and a Predictability of the mode of action of a particular dispersant some of its properties is not conclusively possible. So the specialist is still dependent on him accessible polymers and their derivatives individually or in a package with to try other additives.

The technical processes for the preparation of the polymers however, due to the cationic reaction mechanism in usually statistically composed polymer mixtures, so only a limited variety of products with specific ones chemical and physical properties. These properties can subsequently only be used within narrow limits, for example by distillation and derivatization.

Polymers with M _N <500 daltons in the polymer used generally lead to an increased gas-phase reaction in the thermal ene reaction with maleic anhydride, to a reduced conversion of the higher homologues and to an increased tar formation.

There was therefore interest in a process which starting from the polymers leads to polymers, which new ones or have improved application properties.

Accordingly, the object of the present invention was Process for the preparation of such polymers and their derivatives for the to provide the stated purposes.

• a) das Polymerisat mit einem darin unlöslichen oder wenig löslichen Lösungsmittel mit einem E_T(30)-Wert von 38 bis 57 kcal/mol oder mit einem Gemisch aus zwei oder mehreren solcher Lösungsmittel behandelt,
• b) die dabei entstehende Raffinatphase und Extraktphase voneinander trennt und gewünschtenfalls vom Lösungsmittel befreit.

This object is achieved by a process for the production of raffinates and extracts of such polymers with M _N of 500 to 5000 Daltons, as they arise in the cationic polymerization of alkenes with essentially four carbon atoms, the polymers and extracts consisting predominantly of monoalkenes, by one

• a) treating the polymer with an insoluble or sparingly soluble solvent with an _ET (30) value of 38 to 57 kcal / mol or with a mixture of two or more such solvents,
• b) the resulting raffinate phase and extract phase are separated from one another and, if desired, freed from the solvent.

Furthermore, the task solution found includes those obtained in this way new raffinates and extracts, certain derivatives of these products as well as the use of these raffinates, extracts and derivatives as Auxiliaries in fuels and lubricants. Furthermore, the Invention of such fuels and lubricants.

It has been found that the proportion of polymers with M _N <1000 daltons, preferably M _N <500 daltons, in the polymer can normally be significantly reduced by the process according to the invention.

In practice, they are often in one and the same Production plant made different polymers, the Product specification usually about the reaction conditions is controlled. When changing products, however, usually Parts of the facility will be temporarily shut down, causing the Analagen capacity decreases, and the product quality corresponds to Parking and often not in the subsequent start-up phase the specification. The same applies to a product change in ongoing operations, which often do not involve large quantities Specified goods arise.

Those serving as starting materials in the process according to the invention Polymers can start from a single alkene or from a mixture of two or more alkenes become. The alkenes can also contain fewer or more alkenes Carbon atoms may be accompanied, some or all can react with to the polymer. Preferred starting materials are alkenes with four carbon atoms, preferably 1-butene and 2-butene and especially isobutene, and mixtures of these alkenes. The Proportion of alkenes with four carbon atoms in the total the reactive alkenes used are usually greater than 70 and preferably greater than 85% by weight.

It can also be used for the production of the polymers alkene stream used still further, under the reaction conditions contain inert substances, especially saturated ones Hydrocarbons, especially those with four carbon atoms. In such Mixtures the proportion of alkenes is preferably more than 35 and particularly preferably more than 70% by weight. A technical product of such a nature is raffinate I, which in the chemical industry is available in large quantities and above all Has alkenes and alkanes with four carbon atoms.

As catalysts for the cationic polymerization of alkenes Lewis acids are generally suitable, preferably inorganic Lewis acids such as titanium tetrachloride and boron trichloride.

The method according to the invention proves to be special advantageous if it is applied to polymers, which by Conversion of practically pure isobutene or of raffinate I in Presence of boron trifluoride can be obtained. It is also suitable is particularly good for so-called highly reactive polyisobutenes, which typically have a content greater than 60, and preferably more than 80% by weight of terminal polymers ("Vinylidene -") have double bonds (cf. EP-A 628 575). The Manufacturing processes for such polymers are otherwise Known to those skilled in the art and therefore require no further explanation (see, for example, K. Matyjaszewski (ed.), "Cationic Polymerizations ", Marcel Dekker Inc., New York 1996, pages 684-703).

Suitable solvents for the extraction according to the process according to the invention have an _ET (30) value in the range from 38 to 57 kcal / mol. The E _T (30) value indicates according to Liebigs Ann. Chem. 1983, pages 721-743, the polarity of a solvent or a solvent mixture at 30 ° C. Solvents whose E _T (30) value is from 39 to 43 kcal / mol are preferably used in the process according to the invention. Preferred such solvents are alcohols, nitriles, ketones, esters and ethers. Of these, the aprotic solvents such as dialkyl ketones and alkyl nitriles and in particular acetone and methyl ethyl ketone are particularly preferred. Mixtures of these solvents are also suitable.

Incidentally, those of the solvents mentioned are for the Use particularly preferred in the process according to the invention, which is as short as possible at the end of the extraction step Separate time as much as possible as a separate phase and in particular no difficult to break emulsions with other accruing ones Form phases.

As a rule, 30 to 5000, preferably 50 to 3000, are used, in particular 100 to 5000 wt .-% solvent based on that Weight of the polymers of the mass 500 to 5000 daltons in polymer used or in its derivative used.

The method according to the invention is generally carried out in such a way that that you first the raw or, for example, by distillation pretreated polymer brings together with the solvent and in thoroughly mixed in a manner known per se.

The temperature of the mixing process is preferably from -100 to 200, especially at 0 to 150 and especially at 10 to 100 ° C, the boiling point of the solvent used mainly at Using printing equipment is usually not a problem prepares. Incidentally, the pressure during the extraction is not critical and is generally between 1 and 20 bar.

The duration of the mixing process is usually without More from the respective task and is based in usually on the viscosity and the entered mixing energy. It should be dimensioned at least in such a way that Substance distribution equilibrium regarding the extractable substances between Polymer and solvent can adjust. They tend to separating substances to form emulsions are long Mixing times with low energy input preferred.

At the end of the mixing process, the mixture is let in Split phases. This generally creates one Low-solvent polymer phase (hereinafter referred to as "raffinate phase") called), in which the extractable with the solvent Components in the raw material used are depleted. In addition, one generally obtains a low-polymer phase, which essentially from solvent and the extracted substances exists (hereinafter referred to as "extract phase").

By adding a polar solvent like methanol, Acetonitrile and especially water to the polymer-poor extract phase can often the formation of a polymer-rich phase again are supported or effected, the extract phase usually contains significantly less polymer than the first extract phase. The The amount of such a polar solvent added is Generally 0.5 to 50, preferably 1 to 20 and in particular 2 to 10% by weight based on the extract phase. The polar solvent is usually solved mainly in the extract phase.

Following the separation of the extract phase, the remaining raffinate phase again, also several times, the inventive Procedure. By varying the invention The solvent used can obtain extract phases which are usually in their composition clearly differ from that of the first extraction.

The separation of raffinate phase and extract phase can be started in perform in a known manner and usually by low Support temperatures in the mixture. The energy expenditure for the cooling can be done in particular by technology Suitable cold recovery devices in one keep economically reasonable framework.

Preferred devices for mixing with subsequent In technology, phase separation are so-called mixer settlers.

Solvent fractions can be obtained from the raffinate phase or phases remove in a known manner, especially by distillation. In particular, you can use viscous, pasty or solid Residues for this purpose a non-polar solvent, for example a Add alkane such as hexane or heptane as an entrainer, followed by one as completely as possible - if necessary at reduced pressure - distilled off.

The products obtained in this way are described in the following Phase from which they were obtained as raffinates or extracts. Raffinate, which in turn is made up of Extracts obtained are also called extracts here.

The raffinates and extracts are suitable as such Ingredients of "lubricating oils" (motor oils, hydraulic oils, insulating oils, Gear oils), fuels and adhesives and sealants. In addition, they can serve as starting materials for derivatives, which can be used in the same area of application as those polymers from which they were obtained.

Preferred such derivatives are alcohols, aldehydes, Halides, amines, acids, acid anhydrides, esters, alkylphenols and Mannich bases.

The raffinates and extracts are used to produce these derivatives with inorganic or low molecular weight organic agents such as Maleic anhydride, carbon monoxide, hydrogen, ammonia, Oxygen, peroxides, sulfur dioxide, alcohols, (Poly) ethylene glycol, phenol, formaldehyde and polyamines reacted.

The process according to the invention is also suitable for the production of raffinates of the above-mentioned derivatives of the polymers. In the production of raffinates from PIBSA in particular, a polymer fraction with 90% PIBSA functionality can be extracted from technical 85% goods, while the remaining raffinate of M _N = 2000 has a degree of PIBSA functionalization of only 72%. In particular, that part of the polymer of the derivative which has not been converted in the preparation of these derivatives remains predominantly in the raffinate.

Preferred solvents when applying the process according to the invention to the derivatives are aprotic and polar solvents such as ethers, ketones, nitriles and esters with E _T values of 38 to 57 kcal / mol, preferably those which have considerable gaps in the mixture with the derivative and the one on which it is based Have polymer.

The process according to the invention is particularly suitable for the production of products with particularly high contents of alkenes with terminal double bonds, for example highly reactive polyisobutenes, and for the production of products with values for M _N or M _W which were not previously accessible.

It is also essential, however, that the molecular weight distribution M _W / M _N in the starting material is significantly wider than that of the raffinate. Therefore, the dispersing effect of the imides, which are derived, for example, from a PIBSA and tetraethylene pentamine produced in accordance with the invention, in multi-grade engine oil already reaches an optimum with a PIPSA: amine molar ratio of 1.5: 1 with low thickening, whereas with untreated PIBSA a PIPSA: amine Mol ratio of 2.4: 1 is required.

It was also found that a polyisobutene with M _N = 2300 was obtained from a polyisobutene with M _N = 1000 and a proportion of terminal double bonds of 90% and more, which had been prepared according to WO-A 99/64482, using the process according to the invention could be, which has more than 90% terminal double bonds. In contrast, a product with M _N = 2300, which had been produced in accordance with WO-A 99/64482, had only a proportion of 80 to 85% of terminal double bonds. Starting from M _N = 2300, a proportion of terminal double bonds of 85% was accessible in a corresponding manner using the method according to the invention even for a product with M _N = 5000.

The method according to the invention allows in a Production plant to permanently produce a single polymer, which then according to the invention in fractions with different Split application properties and thus uses becomes.

The method according to the invention is therefore an important addition the known processes for the preparation of polymers, because it increases the product variety of the polymers.

The raffinates obtainable by the process according to the invention, Extracts and derivatives are suitable as additives (auxiliary substances) for fuel, lubricant, explosives, adhesives and Sealant additives, also adhesives and sealants, emulsifiers, Lubricants, surfactants and prepolymers or them are intermediate products for such additives. You have in Molecular weight range above that of the starting material in the Usually lower viscosities, below that higher viscosities.

In a further embodiment, the invention Processes can also be used from the source materials serving polymers to separate those substances which are not were implemented to the polymers.

Examples 3 Substances used

Polyisobutene ("PIB"): The polyisobutene used was prepared in accordance with EP-A 628 575, Example 1 (molecular weight M _N = 2300) and in accordance with WO-A 99/64482, Example 1 (molecular weight M _N = 1000).

Hydroformylated polyisobutene ("PIB-Oxo"): PIB-Oxo was prepared according to EP-A 244 616, Example 1; Hydrogenation under Use 100 g of Raney nickel at a hydrogen pressure of 200 bar without added ammonia.

Polyisobutenamine ("PIBA"): PIBA was produced from PIB with M _N = 1000 according to EP-A 244 616, Example 1.

The number average (M _N ) of the polymers prepared according to the examples were determined by means of gel permeation chromatography, polyisobutenes with defined known values M _{N being used} for the calibration. From the chromatograms obtained, M became _N according to the equation


calculated, is on the C _i in each case a single concentration for the polymer species i in the polymer mixture, and wherein M _{i is} the molecular weight of these individual polymer species i.

The dispersity D was calculated from the ratio of weight average (M _W ) and number average according to the equation


calculated.

The weight average M _W required for this was obtained from the chromatograms obtained using the formula


receive.

The content of terminal vinylidene groups was determined by means of ¹³ C-NMR spectroscopy, using dimerized chloroform as the solvent and tetramethylsilane as the standard.

The viscosities were determined using an Ubbelohde viscometer DIN EN ISO 3104 and a CCS viscometer (Cold Cranking Simulator) according to DIN 51377.

example 1

10 g of a polyisobutene prepared according to EP-A 628 575 with M _N = 2300, D = 1.85, a viscosity at 100 ° C. of 1600 mm ² / s and a content of polymers with terminal double bonds of 81% were in a glass flask of 2000 ml capacity with 990 g of methyl ethyl ketone. The mixture was then heated to 80 ° C. on a rotary evaporator for 30 minutes, the speed of rotation of the rotary evaporator being adjusted so that two emulsified phases formed in the flask. The rotary evaporator was then switched off and the mixture was allowed to cool to 50 ° C., the two emulsified phases being more separated and the raffinate phase becoming completely clear. After 16 hours, the lower phase with the raffinate was separated from the upper phase with the extract using a separatory funnel, evaporated on a rotary evaporator at 150 ° C., then mixed with 100 ml of n-heptane and again evaporated on a rotary evaporator at 150 ° C. The degassing was continued at 150 ° C. and 1 mbar for 30 minutes, and further volatile constituents were removed from the refined polymer thus obtained.

The upper phase, which mainly consists of solvent and the extract, was evaporated analogously to the raffinate procedure and in this way virtually all of the solvent was removed. Table 1 shows the result of the analysis of the polyisobutene, raffinate and extract used. Table 1

Example 2

30 g of a polyisobutene prepared according to EP-A 628 575, Example 5 with M _N = 1000, D = 1.55, a viscosity at 100 ° C. of 200 mm ² / s and a content of polymers with terminal double bonds of 95% were mixed with 970 g of methyl ethyl ketone in a glass flask of 2000 ml capacity. The mixture was then heated to 80 ° C. on a rotary evaporator for 30 minutes, the speed of rotation of the rotary evaporator being set such that two coherent phases with little emulsified components formed in the flask. The mixture was then allowed to cool to 20 ° C. in 16 hours, the clear, supernatant phase was separated from the polymer-rich phase (“raffinate”) and the phase thus removed was cooled to -40 ° C.: that after 24 hours at -40 ° C The lower phase ("raffinate / extract"), which was also separated from the polymer and was separated from it, was separated from its overhanging phase ("extract") by means of a separating funnel.

The 3 phases "raffinate", "raffinate / extract" and "extract" were each evaporated at 150 ° C. on a rotary evaporator, degassed at 1 mbar for 15 min, taken up in 100 ml of n-heptane, evaporated again at 150 ° C. and at this Temperature at a pressure of 1 mbar 30 min freed from other volatile constituents. Table 2 shows the result of the analysis of the starting material and the products obtained. Table 2

Example 3 Manufacture of PIBSA Example 3a Preparation of PIBSA from the raffinate of Example 1

600 g of one obtained from the raffinate phase according to Example 1 Polyisobutene was combined with 1% by weight of 2-propanol in one 1.2 l stirred autoclaves made of V2A steel under a vacuum of 10 mbar set and heated to 225 ° C.

The vacuum line was closed at 160 ° C., and during the Heating to 225 ° C was 66 g melted Maleic anhydride added. The contents of the autoclave were still at 4 hours 225 ° C stirred. Then the heating of the autoclave was switched off, the autoclave carefully with approx. 1.5 to 2.5 bar overpressure relaxed, and at a temperature of 200 ° C a vacuum of 1 mbar. In this way, up to a pressure of 1 mbar of unreacted maleic anhydride removed.

Example 3b Preparation of PIBSA from the raffinate of Example 2

The procedure was as in Example 3a, but the raffinate used according to Example 2.

Table 3 compares the analytical data of the products from Example 3a and Example 3b with that of a PIBSA which was obtained from polyisobutene according to EP-A 628 575, Example 1. Table 3

Example 4 Extractions according to the invention on PIBSA, PIB-Oxo and PIB-amine Example 4a PIBSA

100 g of PIBSA from PIB with M _N = 1000 of Table 2 ("polyisobutene used") were reacted analogously to Examples 3a and 3b with 10% by weight of maleic anhydride based on the total mixture and with 1200 g of acetone in a glass flask of 2000 ml capacity Rotary evaporator heated to 60 ° C, the speed was chosen so that two emulsified phases were formed. The mixture was then allowed to cool to 40 ° C., and after 2 hours the two phases formed were separated into a lower raffinate phase and an upper extract phase, these were evaporated separately, taken up in each case with 200 ml of n-heptane and again each time evaporated to a temperature of 150 ° C and 1 mbar.

Example 4b PIB-oxo

Starting from 100 g PIB-Oxo instead of PIBSA, as in Example 4a continued.

Example 4c PIBA

Starting with 100 PIB amine instead of PIBSA, as in Example 4a continued.

The results and measured analysis data obtained in Examples 4a-4c are summarized in Table 4.

Example 5 Imidation of PIBSA ("Ashless Dispersants") Example 5a Production of "Additive C"

15 g of PIBSA from Example 3b were mixed with tetraethylene pentamine molar ratio PIBSA: tetraethylene pentamine of 2: 1 added and on a rotary evaporator under nitrogen for 4 hours Heated 180 ° C. A pressure of 1 mbar was then applied for 15 minutes created. Using SN 100 (a common low-viscosity mineral oil) the product thus obtained was placed on a solution which Contained 60 wt .-% polymer.

Example 5b

Starting from 15 g of PIBSA raffinate according to Example 4a instead of PIBSA from Example 3b was carried out as in Example 5a. The PIBSA: tetraethylene pentamine ratio was 2: 1.

Example 5c

Starting from 15 g of PIBSA extract according to Example 4a instead of PIBSA from Example 3b was carried out as in Example 5a. The PIBSA: tetraethylene pentamine ratio was 2: 1.

Example 5d

Starting from 15 g of PIBSA raffinate according to Example 4a instead of PIBSA from Example 3b was carried out as in Example 5a. The PIBSA: tetraethylene pentamine ratio was 1.5: 1.

comparison

Based on 20 g PIBSA, the fractionation feed according to Example 4a, the procedure was as in Example 5a. The molar PIBSA: tetraethylene pentamine ratio was 2: 1.

Example 6 Testing the application properties of succinimides from example 5 Additive A

The products from Examples 5b and 5c were in Weight ratio 40: 60 based on PIBSA mixed. Through the Imidation with tetraethylene pentamine changed that corresponding weight ratio of the 60% solutions to 39.1: 60.9. There were 10 g from Example 5b with 15.6 g from Example 5c mixed.

Additive B

The products from Examples 5d and 5c were in Weight ratio 40: 60 based on PIBSA mixed. Through the Imidation with tetraethylene pentamine changed that corresponding weight ratio of the 60% solutions to 39.65: 60.35.

There were 10 g from Example 5d with 15.22 g from Example 5c mixed.

Example 6a Viscosity-temperature behavior

The test was carried out on an engine oil of type 5W30 with the following composition:
Additive A, B or C. 6% by weight PAO 6 47.799% by weight PAO 4 30% by weight Glissofluid® A9 10% by weight Glissoviscal® PG 0.7% by weight Overbased sulfonate 3% by weight ZnDTPs 1.8% by weight Antioxidant 0.5% by weight Friction modifier 0.2% by weight foam inhibitor 0.001% by weight

Table 5 shows the test results. Table 5

Table 5 shows that additives A, B and C according to the invention have lower CCS values in comparison.

Example 6b dispersing

To evaluate the dispersing effect, a spot test was carried out in accordance with "Les Huiles pour Moteurs et al Graissage des Moteurs" by A. Schilling, Vol. 1, page 89 ff. 1962. For this purpose, a diesel carbon black oil dispersion with a content of 3% by weight of the additive to be tested was produced. A drop of the dispersion was applied to a filter paper for paper chromatography and the soot migration was assessed visually on a scale from 0 to 1000. The higher the value, the better the dispersing effect. Table 6 shows the results. Table 6

Table 6 shows that the additives according to the invention, which by extractive fractionation of the PIBSA stage, separated Imidation and reassembly were obtained, dispersants with improved dispersibility at low and high Engine operating temperatures are. In addition, it has been successful with the raffinate the basic nitrogen content by the Molar ratio 1: 1.5 increase, reducing the basicity reserves climb.

Claims (12)

1. A process for the preparation of raffinates and extracts of such polymers with M _N of 500 to 5000 daltons, such as those formed in the cationic polymerization of alkenes with essentially four carbon atoms, the polymers and extracts consisting predominantly of monoalkenes, characterized in that you a) treating the polymer with an insoluble or sparingly soluble solvent with an _ET (30) value of 38 to 57 kcal / mol or with a mixture of two or more such solvents, b) the resulting raffinate phase and extract phase are separated from one another and, if desired, freed from the solvent. 2. The method according to claim 1, characterized in that one uses solvents with an E _T (30) value of 39 to 43 kcal / mol. 3. The method according to claim 1 or 2, characterized in that the polymer multiple times with the same or with various solvents or solvent mixtures extracted according to claim 1. 4. Raffinates, obtainable by the process according to the claims 1 to 3. 5. extracts, obtainable by the process according to the claims 1 to 3. 6. Process for the preparation of derivatives of the raffinates according to Claim 4 and extracts according to claim 5, characterized characterized in that the raffinates and / or the extracts in at known way with inorganic or low molecular weight organic agents. 7. Derivatives obtainable by the process according to claim 6. 8. Use of the raffinates, the extracts and / or the derivatives according to claims 4, 5 or 7, individually or in a mixture, as auxiliary substances. 9. Use of the raffinates, the extracts and / or the derivatives according to claims 4, 5 or 7, individually or in a mixture, as auxiliary substances in fuels. 10. Use of the raffinates, the extracts and / or the derivatives according to claims 4, 5 or 7, individually or in a mixture, as auxiliary substances in lubricants. 11. Fuels containing one or more raffinates, Extracts and / or derivatives according to claims 4, 5 or 7. 12. Lubricants containing one or more raffinates, Extracts and / or derivatives according to claims 4, 5 or 7.