EP1746146A1 - Copolymers based on olefins and ethylenically unsaturated carboxylic acid esters as pour point depressants for fuels and lubricants - Google Patents

Abstract

New copolymer (I) is derived from monomers comprising M1, M2, optionally M3 and optionally M4, where M1 is a mono- or diester of (substituted) maleic or fumaric acid, M2 and M3 are different 2-50 carbon olefins and M4 is (substituted) maleic anhydride. New copolymer (I) is derived from monomers comprising M1, M2, optionally M3 and optionally M4, where M1 is a mono- or diester of (substituted) maleic or fumaric acid of formula (M1), M2 and M3 are different 2-50 carbon olefins and M4 is (substituted) maleic anhydride of formula (M4): [Structures (M1), line 21, and structures (M4), line 41, claim 1, page 18] R1>, R2>H or 1-4 C hydrocarbyl in one case and -COOR5> in the other; R3>, R4>H or 1-4 C hydrocarbyl in one case and -COOR6> in the other; R5>H or 1-40 C hydrocarbyl; R6>1-40 C hydrocarbyl; R7>, R8>H or 1-4 C hydrocarbyl . Independent claims are included for the following: (1) use of a copolymer (I) for as cloud point depressant (CPD) for fuel oils and lubricants; (2) fuel oil composition containing a major weight fraction of middle distillate fuel boiling in the 120-500[deg]C range and a minor fraction of copolymer(s) (I); (3) lubricant composition containing a major weight fraction of a conventional lubricant and a minor fraction of (I); (4) additive package containing (I) in combination with other conventional lubricant or fuel oil additive(s).

Description

The invention relates to the use of copolymers which, in addition to ethylenically unsaturated esters of dicarboxylic acids in copolymerized form contain at least one olefin and optionally the anhydride of an ethylenically unsaturated dicarboxylic acid in order to lower the CP value of fuel oils and lubricants. In addition, the invention relates to such copolymers and with these copolymers additivierten fuel oils and lubricants and additive packages containing such copolymers.

State of the art

Paraffinic wax-containing mineral oils, such as middle distillates, e.g. Diesel and fuel oils show a significant deterioration of the flow properties when the temperature is lowered. The reason for this lies in the crystallization of longer-chain paraffins occurring from the temperature of the cloud point, which form large, platelet-shaped wax crystals. These wax crystals have a sponge-like structure and lead to the inclusion of other fuel constituents in the crystal composite. The appearance of these crystals quickly leads to the bonding of fuel filters both in tanks and in motor vehicles. At temperatures below the pour point (PP), finally, no more flow of fuel takes place.

In the case of middle distillates, the Cloud Point (CP, ASTM D 2500) and the Wax Appearance Temperature (WAT, ASTM D 3117) are the measure of their low-temperature stability. Middle distillates, such as diesel and fuel oil, consist of multi-component systems of hydrocarbons with different chain length and branching. The cloud point is higher, the more long-chain n-paraffins, which are made responsible for the crystallization start, are included in the middle distillate. In order to ensure the quality and manageability of heating oil, according to DIN 51 603-1, its CP value must not exceed 3 ° C. Although a corresponding specification for diesel fuel according to EN 590 does not exist for moderate climatic conditions, certain requirements for the CP value are also made here depending on region and season (for example German winter diesel: CP = -7 ° C).

On the other hand, many refineries have an interest in blending long chain n-paraffins, which are often part of substandard product streams to use higher value in middle distillates. In order for the CP value to still meet the above-mentioned requirements, it will generally be necessary to add an additive to these blends, which lowers the CP.

However, the currently available commercially available CP point depressants (CPD) are of low potency and must therefore be used in high concentrations for any effect to occur (at least 500 ppm). These high concentrations have the disadvantage over the cost that, in particular, they adversely affect the effectiveness of additives that are intended to lower the Cold Filter Plugging Point (CFPP) and are usually added to the middle distillates.

The WO 01/04238 describes the use of copolymers of C ₁₄ -C ₁₆ α-olefins and maleic imides or of terpolymers of ethylene, vinyl acetate and isobutene as CPD. The stated dosing rates are 500 ppm and are therefore very high.

The EP-A-0214786 describes the use of copolymers which contain polymerized in addition to α-olefins with an alcohol esterified maleic anhydride, as a cold flow improver for fuels, eg for lowering the CP and the CFPP value.

There is a need for additives that more effectively decrease the CP value of fuel oils and lubricants, for example, by achieving the same effect as the additives of the prior art at lower dosage rates. In addition, the additives should have an improved formability and with other additives, which are usually added to the fuel oils and lubricants, not enter negative interactions. In particular, they should not adversely affect the effect of CFPP additives.

Brief description of the invention

It is accordingly an object of the present invention to provide additives which satisfy the above requirements.

Surprisingly, this object has been achieved by the unexpected observation that copolymers containing esters of ethylenically unsaturated dicarboxylic acids, at least one olefin and optionally the anhydride of an ethylenically unsaturated dicarboxylic acid in copolymerized form, effectively lower the CP value of fuel oils and lubricants.

worin

R¹ und

R² für H, C₁-C₄-Hydrocarbyl oder -COOR⁵ stehen, wobei einer der Reste R¹ und R² für H oder C₁-C₄-Hydrocarbyl steht und der andere Rest für -COOR⁵ steht;

R³ und

R⁴ für H, C₁-C₄-Hydrocarbyl oder -COOR⁶ stehen, wobei einer der Reste R³ und R⁴ für H oder C₁-C₄-Hydrocarbyl steht und der andere Rest für -COOR⁶ steht;

R⁵

für H oder C₁-C₄₀-Hydrocarbyl steht; und

R⁶

für C₁-C₄₀-Hydrocarbyl steht; und

M2 und M3 für verschiedene ethylenisch ungesättigte C₂-C₅₀-Kohlenwasserstoffe stehen; und
M4 die folgende allgemeine Struktur besitzt:

worin
R⁷ und R⁸ unabhängig voneinander für H oder C₁-C₄-Hydrocarbyl stehen,
zur Erniedrigung des CP-Wertes von Brennstoffölen und Schmierstoffen.A first aspect of the invention accordingly relates to the use of a copolymer which is made up of monomers comprising M1, M2, optionally M3 and optionally M4, where M1 has the following general structure:

wherein

R ¹ and

R ^{2 is} H, C ₁ -C ₄ -hydrocarbyl or -COOR ⁵ , where one of R ¹ and R ^{2 is} H or C ₁ -C ₄ -hydrocarbyl and the other radical is -COOR ⁵ ;

R ³ and

R ^{4 is} H, C ₁ -C ₄ -hydrocarbyl or -COOR ⁶ , where one of R ³ and R ^{4 is} H or C ₁ -C ₄ -hydrocarbyl and the other radical is -COOR ⁶ ;

R ⁵

is H or C ₁ -C ₄₀ hydrocarbyl; and

R ⁶

is C ₁ -C ₄₀ hydrocarbyl; and

M2 and M3 are different ethylenically unsaturated C ₂ -C ₅₀ hydrocarbons; and
M4 has the following general structure:

wherein
R ⁷ and R ^{8 are} independently H or C ₁ -C ₄ hydrocarbyl,
for lowering the CP value of fuel oils and lubricants.

Another object of the invention is such a copolymer. The invention further provides the fuel oils additized with these copolymers and Lubricants. Finally, the invention relates to additive packages containing such copolymers.

Detailed description of the invention

• C₁-C₄₀-Hydrocarbyl steht für einen Kohlenwasserstoffrest mit 1 bis 40 Kohlenstoffatomen. Bevorzugt handelt es sich um einen aliphatischen Kohlenwasserstoffrest, wie C₁-C₄₀-Alkyl, C₂-C₄₀-Alkenyl, C₄-C₄₀-Alkadienyl, C₆-C₄₀-Alkatrienyl, C₈-C₄₀-Alkatetraenyl oder Alkinyl. Insbesondere steht C₁-C₄₀-Hydrocarbyl für C₁-C₄₀-Alkyl.
• C₁-C₄₈-Hydrocarbyl steht für einen Kohlenwasserstoffrest mit 1 bis 48 Kohlenstoffatomen. Bevorzugt handelt es sich um einen aliphatischen Kohlenwasserstoffrest, wie Alkyl, Alkenyl, Alkadienyl, Alkatrienyl, Alkatetraenyl oder Alkinyl. Insbesondere steht C₁-C₄₈-Hydrocarbyl für C₁-C₄₈-Alkyl.
• C₈-C₄₀-Hydrocarbyl steht für einen Kohlenwasserstoffrest mit 8 bis 40 Kohlenstoffatomen. Bevorzugt handelt es sich um einen aliphatischen Kohlenwasserstoffrest, wie Alkyl, Alkenyl, Alkadienyl, Alkatrienyl, Alkatetraenyl oder Alkinyl. Insbesondere steht C₈-C₄₀-Hydrocarbyl für C₈-C₄₀-Alkyl.
• C₈-C₄₈-Hydrocarbyl steht für einen Kohlenwasserstoffrest mit 8 bis 48 Kohlenstoffatomen. Bevorzugt handelt es sich um einen aliphatischen Kohlenwasserstoffrest, wie Alkyl, Alkenyl, Alkadienyl, Alkatrienyl, Alkatetraenyl oder Alkinyl. Insbesondere steht C₈-C₄₈-Hydrocarbyl für C₈-C₄₈-Alkyl.
• C₁-C₁₀-Hydrocarbyl steht für einen Kohlenwasserstoffrest mit 1 bis 10 Kohlenstoffatomen. Bevorzugt handelt es sich um einen aliphatischen Kohlenwasserstoffrest, wie Alkyl, C₂-C₁₀-Alkenyl, C₄-C₁₀-Alkadienyl, C₆-C₁₀-Alkatrienyl, C₈-C₁₀-Alkatetraenyl oder Alkinyl. Insbesondere steht C₁-C₁₀-Hydrocarbyl für C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sec-Butyl, Isobutyl, tert-Butyl, Pentyl, Neopentyl, Hexyl, Heptyl, Octyl, 2-Ethylhexyl, Neooctyl, Nonyl, Neononyl, Decyl, Neodecyl und deren Konstitutionsisomere.
• C₁-C₄₀-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 1 bis 40 Kohlenstoffatomen, wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sec-Butyl, Isobutyl, tert-Butyl, Pentyl, Neopentyl, Hexyl, Heptyl, Octyl, 2-Ethylhexyl, Neooctyl, Nonyl, Neononyl, Decyl, Neodecyl, Undecyl, Neoundecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl, Hencosyl, Docosyl, Tricosyl, Tetracosyl, Pentacosyl, Hexacosyl, Heptacosyl, Octacosyl, Nonacosyl, Squalyl, deren Konstitutionsisomere, höheren Homologen mit 31 bis 40 Kohlenstoffatomen sowie die dazugehörigen Konstitutionsisomere. C₁-C₄-Hydrocarbyl steht für einen Kohlenwasserstoffrest mit 1 bis 4 Kohlenstoffatomen. Bevorzugt handelt es sich um einen aliphatischen Kohlenwasserstoffrest, wie Alkyl, Alkenyl, Alkadienyl oder Alkinyl. Insbesondere steht C₁-C₄-Hydrocarbyl für C₁-C₄-Alkyl, wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sec-Butyl, Isobutyl und tert-Butyl.
• C₁-C₄₈-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 1 bis 48 Kohlenstoffatomen Beispiele hierfür sind neben den zuvor genannten C₁-C₄₀-Alkylresten die höheren Homologen mit 41 bis 48 Kohlenstoffatomen sowie die dazugehörigen Konstitutionsisomere.
• C₈-C₃₀-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 8 bis 30 Kohlenstoffatomen. Beispiele hierfür sind Octyl, 2-Ethylhexyl, Neooctyl, Nonyl, Neononyl, Decyl, Neodecyl, Undecyl, Neoundecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl, Hencosyl, Docosyl, Tricosyl, Tetracosyl, Pentacosyl, Hexacosyl, Heptacosyl, Octacosyl, Nonacosyl und Squalyl sowie die dazugehörigen Konstitutionsisomere.
• C₈-C₄₀-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 8 bis 40 Kohlenstoffatomen, wie Octyl, 2-Ethylhexyl, Neooctyl, Nonyl, Neononyl, Decyl, Neodecyl, Undecyl, Neoundecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl, Hencosyl, Docosyl, Tricosyl, Tetracosyl, Pentacosyl, Hexacosyl, Heptacosyl, Octacosyl, Nonacosyl, Squalyl, deren Konstitutionsisomere, höheren Homologen mit 31 bis 40 Kohlenstoffatomen sowie die dazugehörigen Konstitutionsisomere.
• C₆-C₄₀-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 6 bis 40 Kohlenstoffatomen. Beispiele hierfür sind neben den zuvor genannten C₈-C₄₀-Alkylresten Hexyl und Heptyl sowie die dazugehörigen Konstitutionsisomere.
• C₈-C₄₈-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 8 bis 48 Kohlenstoffatomen. Beispiele hierfür sind neben den zuvor genannten C₈-C₄₀-Alkylresten die höheren Homologen mit 41 bis 48 Kohlenstoffatomen sowie die dazugehörigen Konstitutionsisomere.
• C₁₀-C₂₆-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 10 bis 26 Kohlenstoffatomen. Beispiele hierfür sind Decyl, Neodecyl, Undecyl, Neoundecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl, Hencosyl, Docosyl, Tricosyl, Tetracosyl, Pentacosyl und Hexacosyl sowie die dazugehörigen Konstitutionsisomere. C₁₀-C₃₀-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 10 bis 30 Kohlenstoffatomen. Beispiele hierfür sind neben den für C₁₀-C₂₆-Alkyl genannten Beispielen Heptacosyl, Octacosyl, Nonacosyl und Squalyl sowie die dazugehörigen Konstitutionsisomere. C₁₀-C₄₈-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 10 bis 48 Kohlenstoffatomen. Beispiele hierfür sind neben den für C₁₀-C₃₀-Alkyl genannten Beispielen die höheren Homologen mit 31 bis 48 Kohlenstoffatomen sowie die dazugehörigen Konstitutionsisomere.
• C₁₀-C₃₀-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 10 bis 26 Kohlenstoffatomen. Beispiele hierfür sind neben den zuvor genannten C₁₀-C₂₆-Alkylresten Heptacosyl, Octacosyl, Nonacosyl und Squalyl sowie die dazugehörigen Konstitutionsisomere.
• C₁₄-C₃₈-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 14 bis 38 Kohlenstoffatomen. Beispiele hierfür sind Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl, Hencosyl, Docosyl, Tricosyl, Tetracosyl, Pentacosyl, Hexacosyl, Heptacosyl, Octacosyl, Nonacosyl, Squalyl, deren Konstitutionsisomere, höheren Homologen mit 31 bis 38 Kohlenstoffatomen sowie die dazugehörigen Konstitutionsisomere.
• C₁₈-C₂₆-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 18 bis 26 Kohlenstoffatomen. Beispiele hierfür sind Octadecyl, Nonadecyl, Eicosyl, Hencosyl, Docosyl, Tricosyl, Tetracosyl, Pentacosyl und Hexacosyl sowie die dazugehörigen Konstitutionsisomere.
• C₁₈-C₂₈-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 18 bis 28 Kohlenstoffatomen. Beispiele hierfür sind neben den zuvor genannten Beispielen für C₁₈-C₂₆-Alkylreste Heptacosyl und Octacosyl sowie die dazugehörigen Konstitutionsisomere.
• C₁₆-C₂₈-Alkyl steht für einen linearen oder verzweigten Alkylrest mit 16 bis 28 Kohlenstoffatomen. Beispiele hierfür sind neben den zuvor genannten Beispielen für C₁₈C₂₈-Alkylreste Hexadecenyl und Heptadecenyl sowie die dazugehörigen Konstitutionsisomere.
• C₂-C₄₀-Alkenyl ist ein einfach ungesättigter linearer oder verzweigter Kohlenwasserstoffrest mit 2 bis 40 Kohlenstoffatomen. Beispiele hierfür sind Ethenyl, Propenyl, Butenyl, Pentenyl, Hexenyl, Heptenyl, Octenyl, Nonenyl, Decenyl, Undecenyl, Dodecenyl, Tridecenyl, Tetradecenyl, Pentadecenyl, Hexadecenyl, Heptadecenyl, Octadecenyl, Nonadecenyl, Eicosenyl, Hencosenyl, Docosenyl, Tricosenyl, Tetracosenyl, Pentacosenyl, Hexacosenyl, Heptacosenyl, Octacosenyl, Nonacosenyl, Squalenyl, deren Konstitutionsisomere, höheren Homologe mit 31 bis 40 C-Atomen sowie Konstitutionsisomere davon.
• C₄-C₄₀-Alkadienyl ist ein zweifach ungesättigter linearer oder verzweigter Kohlenwasserstoffrest mit 4 bis 40 Kohlenstoffatomen. Die olefinischen Doppelbindungen können konjugiert oder isoliert vorliegen. Beispiele hierfür sind Butadienyl, Pentadienyl, Hexadienyl, Heptadienyl, Octadienyl, Nonadienyl, Decadienyl, Undecadienyl, Dodecadienyl, Tridecadienyl, Tetradecadienyl, Pentadecadienyl, Hexadecadienyl, Heptadecadienyl, Octadecadienyl, Nonadecadienyl, Eicosadienyl, Hencosadienyl, Docosadienyl, Tricosadienyl, Tetracosadienyl, Pentacosadienyl, Hexacosadienyl, Heptacosadienyl, Octacosadienyl, Nonacosadienyl, Squaladienyl, deren Konstitutionsisomere, höheren Homologe mit 31 bis 40 C-Atomen sowie Konstitutionsisomere davon.
• C₆-C₄₀-Alkatrienyl ist ein dreifach ungesättigter linearer oder verzweigter Kohlenwasserstoffrest mit 6 bis 40 Kohlenstoffatomen. Die olefinischen Doppelbindungen können konjugiert oder isoliert vorliegen. Beispiele hierfür sind Hexatrienyl Heptatrienyl, Octatrienyl, Nonatrienyl, Decatrienyl, Undecatrienyl, Dodecatrienyl, Tridecatrienyl, Tetradecatrienyl, Pentadecatrienyl, Hexadecatrienyl, Heptadecatrienyl, Octadecatrienyl, Nonadecatrienyl, Eicosatrienyl, Hencosatrienyl, Docosatrienyl, Tricosatrienyl, Tetracosatrienyl, Pentacosatrienyl, Hexacosatrienyl, Heptacosatrienyl, Octacosatrienyl, Nonacosatrienyl, Squalatrienyl, deren Konstitutionsisomere, höhere Homologe sowie Konstitutionsisomere davon.
• C₈-C₄₀-Alkatetraenyl ist ein vierfach ungesättigter linearer oder verzweigter Kohlenwasserstoffrest mit 8 bis 40 Kohlenstoffatomen. Die olefinischen Doppelbindungen können konjugiert oder isoliert vorliegen. Beispiele hierfür sind Octatetraenyl, Nonatetraenyl, Decatetraenyl, Undecatetraenyl, Dodecatetraenyl, Tridecatetraenyl, Tetradecatetraenyl, Pentadecatetraenyl, Hexadecatetraenyl, Heptadecatetraenyl, Octadecatetraenyl, Nonadecatetraenyl, Eicosatetraenyl, Hencosatetraenyl, Docosatetraenyl, Tricosatetraenyl, Tetracosatetraenyl, Pentacosatetraenyl, Hexacosatetraenyl, Heptacosatetraenyl, Octacosatetraenyl, Nonacosatetraenyl, Squalatetraenyl, deren Konstitutionsisomere, höhere Homologe sowie Konstitutionsisomere davon.
• Bei den ethylenisch ungesättigten Kohlenwasserstoffen mit 2 bis 50 Kohlenstoffatomen handelt es sich vorzugsweise um aliphatische Kohlenwasserstoffe mit einer oder mehreren C-C-Doppelbindungen, wie Alkene, Alkadiene oder Alkatriene. Insbesondere handelt es sich um C₂-C₅₀-Alkene, d.h. um aliphatische Kohlenwasserstoffe mit einer C-C-Doppelbindung und mit 2 bis 50 Kohlenstoffatomen. Die C-C-Doppelbindung in den Alkenen kann dabei sowohl intern als auch terminal angeordnet sein.
• C₂-C₅₀-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 2 bis 50 Kohlenstoffatomen. Beispiele hierfür sind E-then, Propen, 1- und 2-Buten, Isobuten, 1- und 2-Penten, 1-, 2- und 3-Hexen, 1-, 2-und 3-Hepten, 1-, 2-, 3- und 4-Octen, 1-, 2-, 3- und 4-Nonen, 1-, 2-, 3-, 4- und 5-Decen, Undecen, Dodecen, Tridecen, Tetradecen, Pentadecen, Hexadecen, Heptadecen, Octadecen, Nonadecen, Eicosen, Hencosen, Docosen, Tricosen, Tetracosen, Pentacosen, Hexacosen, Heptacosen, Octacosen, Nonacosen, Squalen, Konstitutionsisomere davon, die höheren Homologen mit 31 bis 50 Kohlenstoffatomen sowie die dazugehörigen Konstitutionsisomere. Beispiele für Konstitutionsisomere der genannten Alkene sind Oligomere und Polymere von α-, β-, γ-, δ-, etc. C₃-C₈-Olefinen, wie Propen, 1- oder 2-Buten, Isobuten, 1- oder 2-Penten, 2-Methylbuten, 1-, 2- oder 3-Hexen, 1-, 2- oder 3-Hepten oder 1-, 2-, 3- oder 4-Octen.
• C₁₈-C₂₈-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 18 bis 28 Kohlenstoffatomen. Beispiele hierfür sind Octadecen, Nonadecen, Eicosen, Hencosen, Docosen, Tricosen, Tetracosen, Pentacosen, Hexacosen, Heptacosen, Octacosen und Konstitutionsisomere davon.
• C₁₈-C₃₀-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 18 bis 30 Kohlenstoffatomen. Beispiele hierfür sind neben zuvor genannten C₁₈-C₂₈-Alkenen Nonacosen, Squalen und Konstitutionsisomere davon.
• C₈-C₃₀-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 8 bis 30 Kohlenstoffatomen. Beispiele hierfür sind neben zuvor genannten C₁₈-C₃₀-Alkenen Octen, Nonen, Decen, Undecen, Dodecen, Tridecen, Tetradecen, Pentadecen, Hexadecen, Heptadecen und Konstitutionsisomere davon.
• C₁₆-C₂₆-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 16 bis 26 Kohlenstoffatomen. Beispiele hierfür sind Hexadecen, Heptadecen, Octadecen, Nonadecen, Eicosen, Hencosen, Docosen, Tricosen, Tetracosen, Pentacosen, Hexacosen und Konstitutionsisomere davon.
• C₂₀-C₂₄-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 20 bis 24 Kohlenstoffatomen. Beispiele hierfür sind Eicosen, Hencosen, Docosen, Tricosen, Tetracosen und Konstitutionsisomere davon.
• C₁₀-C₁₄-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 10 bis 14 Kohlenstoffatomen. Beispiele hierfür sind Decen, Undecen, Dodecen, Tridecen, Tetradecen und Konstitutionsisomere davon.
• C₁₂-C₄₀-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 12 bis 40 Kohlenstoffatomen. Beispiele hierfür sind Dodecen, Tridecen, Tetradecen, Pentadecen, Hexadecen, Heptadecen, Octadecen, Nonadecen, Eicosen, Hencosen, Docosen, Tricosen, Tetracosen, Pentacosen, Hexacosen, Heptacosen, Octacosen, Nonacosen, Squalen, Konstitutionsisomere davon, die höheren Homologen mit 31 bis 40 Kohlenstoffatomen sowie die dazugehörigen Konstitutionsisomere.
• C₁₂-C₅₀-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 12 bis 50 Kohlenstoffatomen. Beispiele hierfür sind neben den zuvor genannten C₁₂-C₄₀-Alkenen die höheren Homologen mit 41 bis 50 Kohlenstoffatomen sowie die dazugehörigen Konstitutionsisomere.
• C₁₀-C₅₀-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 10 bis 50 Kohlenstoffatomen. Beispiele hierfür sind neben den zuvor genannten C₁₂-C₅₀-Alkenen 1-, 2-, 3-, 4- und 5-Decen und Undecen sowie die dazugehörigen Konstitutionsisomere.
• C₆-C₅₀-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 6 bis 50 Kohlenstoffatomen. Beispiele hierfür sind neben den zuvor genannten C₁₀-C₅₀-Alkenen 1-, 2- und 3-Hexen, 1-, 2- und 3-Hepten, 1-, 2-, 3- und 4-Octen, 1-, 2-, 3- und 4-Nonen sowie die dazugehörigen Konstitutionsisomere.
• C₃₀-C₅₀-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 30 bis 50 Kohlenstoffatomen. C₃₅-C₄₅-Alken steht für einen einfach ungesättigten aliphatischen linearen oder verzweigten Kohlenwasserstoff mit 35 bis 45 Kohlenstoffatomen.

Unless otherwise specified, the following general definitions apply in the context of the present invention:

• C ₁ -C ₄₀ -hydrocarbyl is a hydrocarbon radical having 1 to 40 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as C ₁ -C ₄₀ -alkyl, C ₂ -C ₄₀ -alkenyl, C ₄ -C ₄₀ -alkadienyl, C ₆ -C ₄₀ -alkatrienyl, C ₈ -C ₄₀ -alkatetraenyl or alkynyl. In particular, C ₁ -C ₄₀ -hydrocarbyl is C ₁ -C ₄₀ -alkyl.
• C ₁ -C ₄₈ -hydrocarbyl is a hydrocarbon radical having 1 to 48 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl, alkatrienyl, Alkatetraenyl or alkynyl. In particular, C ₁ -C ₄₈ -hydrocarbyl is C ₁ -C ₄₈ -alkyl.
• C ₈ -C ₄₀ -hydrocarbyl is a hydrocarbon radical having 8 to 40 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl, alkatrienyl, Alkatetraenyl or alkynyl. In particular, C ₈ -C ₄₀ -hydrocarbyl is C ₈ -C ₄₀ -alkyl.
• C ₈ -C ₄₈ -hydrocarbyl is a hydrocarbon radical having 8 to 48 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl, alkatrienyl, Alkatetraenyl or alkynyl. In particular, C ₈ -C ₄₈ -hydrocarbyl is C ₈ -C ₄₈ -alkyl.
• C ₁ -C ₁₀ -hydrocarbyl is a hydrocarbon radical having 1 to 10 carbon atoms. Preference is given to an aliphatic hydrocarbon radical, such as alkyl, C ₂ -C ₁₀ -alkenyl, C ₄ -C ₁₀ -alkadienyl, C ₆ -C ₁₀ -alkatrienyl, C ₈ -C ₁₀ -alkatetraenyl or alkynyl. In particular, C ₁ -C ₁₀ -hydrocarbyl is C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, neodecyl and their constitutional isomers.
• C ₁ -C ₄₀ -alkyl represents a linear or branched alkyl radical having 1 to 40 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, Hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, squalyl, their constitutional isomers, higher homologues having from 31 to 40 carbon atoms and the associated constitutional isomers. C ₁ -C ₄ -hydrocarbyl is a hydrocarbon radical having 1 to 4 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, C ₁ -C ₄ -hydrocarbyl is C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
• C ₁ -C ₄₈ -alkyl is a linear or branched alkyl radical having 1 to 48 carbon atoms. Examples of these are, in addition to the abovementioned C ₁ -C ₄₀ -alkyl radicals, the higher homologues having 41 to 48 carbon atoms and the associated constitutional isomers.
• C ₈ -C ₃₀ -alkyl represents a linear or branched alkyl radical having 8 to 30 carbon atoms. Examples of these are octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl , Hexacosyl, heptacosyl, octacosyl, nonacosyl and squalyl and the associated constitutional isomers.
• C ₈ -C ₄₀ alkyl represents a linear or branched alkyl radical having 8 to 40 carbon atoms, such as octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl , Heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, squalyl, their constitutional isomers, higher homologues having from 31 to 40 carbon atoms and the associated constitutional isomers.
• C ₆ -C ₄₀ -alkyl represents a linear or branched alkyl radical having 6 to 40 carbon atoms. Examples include, in addition to the aforementioned C ₈ -C ₄₀ -alkyl radicals hexyl and heptyl and the associated constitution isomers.
• C ₈ -C ₄₈ alkyl represents a linear or branched alkyl radical having 8 to 48 carbon atoms. Examples of these are, in addition to the aforementioned C ₈ -C ₄₀ -alkyl radicals, the higher homologues having 41 to 48 carbon atoms and the associated constitutional isomers.
• C ₁₀ -C ₂₆ -alkyl represents a linear or branched alkyl radical having 10 to 26 carbon atoms. Examples of these are decyl, neodecyl, undecyl, neoundecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl and hexacosyl and the associated constitutional isomers. C ₁₀ -C ₃₀ -alkyl represents a linear or branched alkyl radical having 10 to 30 carbon atoms. Examples of these are, in addition to the examples mentioned for C ₁₀ -C ₂₆ -alkyl, heptacosyl, octacosyl, nonacosyl and squalyl, as well as the associated constitutional isomers. C ₁₀ -C ₄₈ alkyl represents a linear or branched alkyl radical having 10 to 48 carbon atoms. Examples include, in addition to the examples mentioned for C ₁₀ -C ₃₀ -alkyl, the higher homologues having 31 to 48 carbon atoms and the associated constitutional isomers.
• C ₁₀ -C ₃₀ -alkyl represents a linear or branched alkyl radical having 10 to 26 carbon atoms. Examples of these are, in addition to the aforementioned C ₁₀ -C ₂₆ -alkyl radicals, heptacosyl, octacosyl, nonacosyl and squalyl, as well as the associated constitutional isomers.
• C ₁₄ -C ₃₈ alkyl represents a linear or branched alkyl radical having 14 to 38 carbon atoms. Examples of these are tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, squalyl, their constitutional isomers, higher homologues having 31 to 38 carbon atoms and the associated constitutional isomers.
• C ₁₈ -C ₂₆ -alkyl represents a linear or branched alkyl radical having 18 to 26 carbon atoms. Examples of these are octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl and hexacosyl and the associated constitutional isomers.
• C ₁₈ -C ₂₈ -alkyl represents a linear or branched alkyl radical having 18 to 28 carbon atoms. Examples include, in addition to the aforementioned examples of C ₁₈ -C ₂₆ -alkyl heptacosyl and octacosyl and the associated constitution isomers.
• C ₁₆ -C ₂₈ -alkyl is a linear or branched alkyl radical having 16 to 28 carbon atoms. Examples of these are, in addition to the aforementioned examples of C ₁₈ C ₂₈ -alkyl radicals hexadecenyl and heptadecenyl and the associated constitutional isomers.
• C ₂ -C ₄₀ alkenyl is a monounsaturated linear or branched hydrocarbon radical having 2 to 40 carbon atoms. Examples of these are ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, Nonadecenyl, eicosenyl, hencosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, squalenyl, their constitutional isomers, higher homologues of 31 to 40 carbon atoms, and constitutional isomers thereof.
• C ₄ -C ₄₀ -alkadienyl is a diunsaturated linear or branched hydrocarbon radical having 4 to 40 carbon atoms. The olefinic double bonds may be conjugated or isolated. Examples include butadienyl, pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadienyl, decadienyl, undecadienyl, dodecadienyl, tridecadienyl, Tetradecadienyl, Pentadecadienyl, Hexadecadienyl, heptadecadienyl, octadecadienyl, Nonadecadienyl, Eicosadienyl, Hencosadienyl, Docosadienyl, Tricosadienyl, Tetracosadienyl, Pentacosadienyl, Hexacosadienyl, Heptacosadienyl , Octacosadienyl, nonacosadienyl, squaladienyl, their constitutional isomers, higher homologues having 31 to 40 carbon atoms, and constitutional isomers thereof.
• C ₆ -C ₄₀ -alkatrienyl is a triunsaturated linear or branched hydrocarbon radical having 6 to 40 carbon atoms. The olefinic double bonds may be conjugated or isolated. Examples include hexatrienyl heptatrienyl, octatrienyl, nonatrienyl, decatrienyl, Undecatrienyl, dodecatrienyl, tridecatrienyl, tetradecatrienyl, Pentadecatrienyl, Hexadecatrienyl, heptadecatrienyl, octadecatrienyl, Nonadecatrienyl, eicosatrienyl, Hencosatrienyl, Docosatrienyl, Tricosatrienyl, Tetracosatrienyl, Pentacosatrienyl, Hexacosatrienyl, Heptacosatrienyl, Octacosatrienyl, Nonacosatrienyl, Squalatrienyl, their constitutional isomers, higher homologs and constitutional isomers thereof.
• C ₈ -C ₄₀ -alkatetraenyl is a quadruply unsaturated linear or branched hydrocarbon radical having 8 to 40 carbon atoms. The olefinic double bonds may be conjugated or isolated. Examples include Octatetraenyl, Nonatetraenyl, Decatetraenyl, Undecatetraenyl, Dodecatetraenyl, Tridecatetraenyl, Tetradecatetraenyl, Pentadecatetraenyl, hexadecatetraenyl, Heptadecatetraenyl, Octadecatetraenyl, Nonadecatetraenyl, eicosatetraenyl, Hencosatetraenyl, Docosatetraenyl, Tricosatetraenyl, Tetracosatetraenyl, Pentacosatetraenyl, Hexacosatetraenyl, Heptacosatetraenyl, Octacosatetraenyl, Nonacosatetraenyl, Squalatetraenyl whose Constitutional isomers, higher homologs and constitutional isomers thereof.
• The ethylenically unsaturated hydrocarbons having 2 to 50 carbon atoms are preferably aliphatic hydrocarbons having one or more CC double bonds, such as alkenes, alkadienes or alkatrienes. In particular, they are C ₂ -C ₅₀ -alkenes, ie aliphatic hydrocarbons having a CC double bond and having 2 to 50 carbon atoms. The CC double bond in the alkenes can be arranged both internally and terminally.
• C ₂ -C ₅₀ -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 2 to 50 carbon atoms. Examples of these are E-then, propene, 1- and 2-butene, isobutene, 1- and 2-pentene, 1-, 2- and 3-hexene, 1-, 2- and 3-heptene, 1-, 2- , 3- and 4-octene, 1-, 2-, 3- and 4-nonene, 1-, 2-, 3-, 4- and 5-decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene , Octadecene, nonadecene, eicosene, hencoses, docoses, tricosene, tetracoses, pentacoses, hexacoses, heptacoses, octacoses, nonacoses, squalene, constitutional isomers thereof, the higher homologues of 31 to 50 carbon atoms and the associated constitutional isomers. Examples of constitutional isomers of said alkenes are oligomers and polymers of α-, β-, γ-, δ-, etc. C ₃ -C ₈ -olefins, such as propene, 1- or 2-butene, isobutene, 1- or 2- Pentene, 2-methylbutene, 1-, 2- or 3-hexene, 1-, 2- or 3-heptene or 1-, 2-, 3- or 4-octene.
• C ₁₈ -C ₂₈ -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 18 to 28 carbon atoms. Examples of these are octadecene, nonadecene, eicosene, hencoses, docoses, tricosene, tetracoses, pentacoses, hexacoses, heptacoses, octacoses and constitutional isomers thereof.
• C ₁₈ -C ₃₀ -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 18 to 30 carbon atoms. Examples of these, in addition to the previously mentioned C ₁₈ -C ₂₈ alkenes, are nonacoses, squalene and constitutional isomers thereof.
• C ₈ -C ₃₀ -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 8 to 30 carbon atoms. Examples thereof include, in addition to the aforementioned C ₁₈ -C ₃₀ alkenes, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene and constitutional isomers thereof.
• C ₁₆ -C ₂₆ -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 16 to 26 carbon atoms. Examples of these are hexadecene, heptadecene, octadecene, nonadecene, eicosene, hencoses, docoses, tricosene, tetracoses, pentacoses, hexacoses and constitutional isomers thereof.
• C ₂₀ -C ₂₄ -alkene represents a monounsaturated aliphatic linear or branched hydrocarbon having 20 to 24 carbon atoms. Examples of these are eicosene, hencoses, docoses, tricos, tetracoses and constitutional isomers thereof.
• C ₁₀ -C ₁₄ -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 10 to 14 carbon atoms. Examples of these are decene, undecene, dodecene, tridecene, tetradecene and constitutional isomers thereof.
• C ₁₂ -C ₄₀ -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 12 to 40 carbon atoms. Examples of these are dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, hencoses, docoses, tricosene, tetracoses, pentacoses, hexacoses, heptacoses, octacoses, nonacoses, squalene, constitutional isomers thereof, the higher homologues with 31 to 40 carbon atoms and the associated constitutional isomers.
• C ₁₂ -C ₅₀ -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 12 to 50 carbon atoms. Examples include, in addition to the aforementioned C ₁₂ -C ₄₀ alkenes, the higher homologues with 41 to 50 carbon atoms and the associated constitutional isomers.
• C ₁₀ -C ₅₀ -alkene represents a monounsaturated aliphatic linear or branched hydrocarbon having 10 to 50 carbon atoms. Examples include, in addition to the aforementioned C ₁₂ -C ₅₀ alkenes 1-, 2-, 3-, 4- and 5-decene and undecene and the associated constitutional isomers.
• C ₆ -C ₅₀ -alkene represents a monounsaturated aliphatic linear or branched hydrocarbon having 6 to 50 carbon atoms. Examples of these are, in addition to the aforementioned C ₁₀ -C ₅₀ -alkenes, 1-, 2- and 3-hexene, 1-, 2- and 3-heptene, 1-, 2-, 3- and 4-octene, 1-, 2-, 3- and 4-nonene and the associated constitutional isomers.
• C ₃₀ -C ₅₀ -alkene represents a monounsaturated aliphatic linear or branched hydrocarbon having 30 to 50 carbon atoms. C ₃₅ -C ₄₅ -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having from 35 to 45 carbon atoms.

The hydrocarbyl radicals, for example the alkyl, alkenyl, alkadienyl, alkatrienyl and alkatetraenyl radicals, or the unsaturated hydrocarbons, for example the alkenes, may be unsubstituted or monosubstituted or polysubstituted. Suitable substituents are, for example, OH, C ₁ -C ₄ -alkoxy, NR ¹⁵ R ¹⁶ (R ¹⁵ and R ¹⁶ are each independently H or C ₁ -C ₄ -alkyl) or carbonyl (COR ¹⁵ ). Preferably, however, they are unsubstituted.

C ₁ -C ₄ alkoxy is a via an oxygen atom bonded C ₁ -C ₄ alkyl radical. Examples of these are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, isobutoxy and tert-butoxy.

C ₁₈ -C ₂₆ -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 18 to 26 carbon atoms, which is substituted by one or more, preferably a hydroxy group. Examples of these are octadecanol, nonadecaol, eicosanol, octadecenol, nonadecenol, eicosenol, octadecadienol, nonadecadienol, eicosadienol, octadecatrienol, nonadecatrienol, eicosatrienol, positional and constitutional isomers thereof, the higher homologues having 21 to 26 carbon atoms and the associated positional and constitutional isomers.

C ₁₆ -C ₂₆ -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 16 to 26 carbon atoms, which is substituted by one or more, preferably a hydroxy group. Examples include, in addition to the aforementioned C ₁₈ -C ₂₆ alcohols, hexadecanol, heptadecanol, hexadecenol, heptadecenol, hexadecadienol, heptadecadienol and the associated positional and constitutional isomers.

C ₁₆ -C ₂₈ -Alcohol is a linear or branched saturated or unsaturated aliphatic hydrocarbon having 16 to 26 carbon atoms, which is substituted by one or more, preferably a hydroxy group. Examples include, in addition to the aforementioned C ₁₈ -C ₂₆ alcohols, the higher homologues having 27 or 28 carbon atoms and the associated position and constitution isomers.

C ₁₀ -C ₂₆ -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 10 to 26 carbon atoms, which is substituted by one or more, preferably a hydroxy group. Examples of these are, in addition to the abovementioned C ₁₈ -C ₂₆ -alcohols, decanol, undecanol, dodecanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, decenol, undecenol, dodecenol, tridecenol, isotridecenol, tetradecenol, pentadecenol, hexadecenol, heptadecenol, Decadienol, undecadienol, dodecadienol, tridecadienol, isotridecadienol, tetradecadienol, pentadecadienol, hexadecadienol, heptadecadienol and the associated positional and constitutional isomers.

C ₁₀ -C ₃₀ -Alcohol is a linear or branched saturated or unsaturated aliphatic hydrocarbon having 10 to 30 carbon atoms, which is substituted by one or more, preferably a hydroxy group. examples for this are in addition to the aforementioned C ₁₀ -C ₂₆ -alcohols, the higher homologues having 27 to 30 carbon atoms and the associated position and constitution isomers.

C ₈ -C ₃₀ -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 8 to 30 carbon atoms, which is substituted by one or more, preferably a hydroxy group. Examples include, in addition to the aforementioned C ₁₀ -C ₃₀ alcohols octanol, 2-ethylhexanol, nonanol, neononyl alcohol, octenol, 2-ethylhexenol, Nonenol and the associated position and constitution isomers.

C ₆ -C ₃₀ -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 6 to 30 carbon atoms which is substituted by one or more, preferably a hydroxy group. Examples include, in addition to the aforementioned C ₈ -C ₃₀ alcohols hexanol and heptanol and the associated position and constitution isomers.

C ₆ -C ₄₀ -Alcohol is a linear or branched aliphatic hydrocarbon having 6 to 40 carbon atoms, which is substituted by one or more, preferably a hydroxy group. Examples include, in addition to the aforementioned C ₆ -C ₃₀ alcohols, the higher homologues having 31 to 40 carbon atoms and the associated position and constitution isomers.

When the copolymer used according to the invention also contains the monomer M3 in copolymerized form, M2 and M3 preferably differ by the number of carbon atoms, the difference preferably being at least 6 carbon atoms. Most preferably, M3 contains a greater number of carbon atoms than M2. In particular, M3 contains at least 6 more carbon atoms than M2.

Preferably, the copolymer contains the monomers M1, M2, optionally M3 and optionally M4 randomly polymerized.

• M1+M4: 0,1 bis 0,7;
• M2: 0,05 bis 0,7;
• M3: 0 bis 0,7;

wobei das Molverhältnis von M1 zu M4 vorzugsweise 1:0 bis 1:1 beträgt; und
wobei die Summe der molaren Anteile von M2 und M3 0,3 bis 0,9 beträgt;
besonders bevorzugt

• M1+M4: 0,2 bis 0,6;
• M2: 0,1 bis 0,6;
• M3: 0 bis 0,5;

wobei das Molverhältnis von M1 zu M4 vorzugsweise 1:0 bis 1:1 beträgt; und
wobei die Summe der molaren Anteile von M2 und M3 0,4 bis 0,8 beträgt;
und insbesondere

• M1+M4: 0,4 bis 0,6;
• M2: 0,2 bis 0,6;
• M3: 0 bis 0,3;

wobei das Molverhältnis von M1 zu M4 vorzugsweise 1:0 bis 1:1 beträgt; und
wobei die Summe der molaren Anteile von M2 und M3 0,4 bis 0,6 beträgt.In the copolymers used according to the invention, the monomers M1, M2, M3 and M4 are preferably present in the copolymer in the following molar proportions (Mx / (M1 + M2 + M3 + M4):

• M1 + M4: 0.1 to 0.7;
• M2: 0.05 to 0.7;
• M3: 0 to 0.7;

wherein the molar ratio of M1 to M4 is preferably 1: 0 to 1: 1; and
wherein the sum of the molar proportions of M2 and M3 is 0.3 to 0.9;
particularly preferred

• M1 + M4: 0.2 to 0.6;
• M2: 0.1 to 0.6;
• M3: 0 to 0.5;

wherein the molar ratio of M1 to M4 is preferably 1: 0 to 1: 1; and
wherein the sum of the molar proportions of M2 and M3 is 0.4 to 0.8;
and particularly

• M1 + M4: 0.4 to 0.6;
• M2: 0.2 to 0.6;
• M3: 0 to 0.3;

wherein the molar ratio of M1 to M4 is preferably 1: 0 to 1: 1; and
wherein the sum of the molar proportions of M2 and M3 is 0.4 to 0.6.

Preferably, the molar fraction of the monomer M3 is lower than that of the monomer M2.

Monomer M1 is a mono- or diester of fumaric acid or maleic acid, optionally substituted on the C-C double bond.

The copolymer used according to the invention may contain, as monomer M1, in copolymerized form monoesters and diesters of ethylenically unsaturated dicarboxylic acids.

In addition, the copolymer used as monomer M1 mono- and / or diesters of ethylenically unsaturated dicarboxylic acids in copolymerized form, which are derived from various alcohols.

R ⁵ is preferably H or C ₁ -C ₄₀ -alkyl, more preferably H or C ₆ -C ₄₀ -alkyl, more preferably H or C ₈ -C ₃₀ -alkyl and especially H or C ₁₀ -C ₃₀ -Alkyl, for example for H or C ₁₀ -C ₂₆ -alkyl or C ₁₈ -C ₂₆ -alkyl.

R ⁶ is preferably C ₁ -C ₄₀ -alkyl, more preferably C ₆ -C ₄₀ -alkyl, more preferably C ₈ -C ₃₀ -alkyl and in particular C ₁₀ -C ₃₀ -alkyl, for example C ₁₀ - C ₂₆ alkyl or C ₁₈ -C ₂₆ alkyl.

The alcohol component of the ester monomer M1 (R ⁶ and optionally R ⁵ ) is derived correspondingly particularly preferably from relatively long-chain alcohols, for example from C ₆ -C ₄₀ -alcohols, preferably from C ₈ -C ₃₀ -alcohols and especially from C ₁₀ - C ₃₀ -alcohols, for example of C ₁₀ -C ₂₆ -alcohols or of C ₁₈ -C ₂₆ -alcohols. It can also be derived from mixtures of such alcohols, for example mixtures obtained from industrial processes, such as fatty alcohols or alcohols from hydroformylation processes.

When R ^{5 is} H, in a preferred embodiment the copolymer also contains, in addition to M 1, M 2 and optionally also M 3, copolymerized monomer M 4.

When the copolymer also contains monomer M4 in copolymerized form, the molar ratio of copolymerized M1 to copolymerized M4 is preferably 20: 1 to 1.5: 1, more preferably 10: 1 to 2: 1, more preferably 8: 1 to 2: 1, in particular 5: 1 to 2: 1 and especially 4: 1 to 2: 1.

In monomer M1, one of the radicals R ¹ or R ² is preferably H, while the other is -COOR ⁵ . Preferably, one of R ³ or R ^{4 is} H while the other is -COOR ⁶ . Accordingly, M1 is preferably an unsubstituted mono- or diester of fumaric acid or maleic acid.

In a particularly preferred embodiment, in the monomer M1 R ¹ and R ^{3 are} H, while R ^{2 is} -COOR ⁵ and R ^{4 is} -COOR ⁶ , ie M1 is particularly preferably a maleic acid mono- or diester.

Particularly preferred monomers M1 are maleic acid monoesters (R ⁵ = H). However, the copolymer may also partially contain maleic diester in copolymerized form.

In this case (ie R ⁵ = H) the above proviso applies, ie the copolymer used according to the invention preferably also contains monomer M 4 in copolymerized form.

If R ^{5 is} not H, then M1 may be both a symmetric and a mixed ester (ie, R ⁵ and R ⁶ may be the same or different).

In an alternatively particularly preferred embodiment, R ^{5 is} not H. The copolymer can of course also contain monomer M4 in copolymerized form. Preferably, however, it does not contain any copolymerized M4 in this case. M1 here is preferably a maleic acid or in particular fumaric diester.

Examples of ester monomers M1 are the monoesters or the symmetrical or mixed diesters of fumaric acid or maleic acid with methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2- Ethylhexanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanot, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, hencosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, squalanol, positional and constitutional isomers and higher homologs and associated position and constitutional isomers. However, as already mentioned, preferred ester monomers M1 are the monoesters or the symmetrical or mixed diesters of fumaric acid or maleic acid with longer-chain alcohols, for example with C ₆ -C ₄₀ -alcohols, particularly preferably with C ₈ -C ₃₀ -alcohols and in particular with C ₁₀ -C ₃₀ -alcohols, for example with C ₁₀ -C ₂₆ -alcohols or with C ₁₈ -C ₂₆ -alcohols.

worin

R⁹ und R¹³

gleich oder verschieden sind und für H oder C₁-C₅₀-Hydrocarbyl stehen; und

R¹⁰, R¹¹, R¹², R¹⁴, R¹⁵ und R¹⁶

gleich oder verschieden sind und für H oder C₁-C₁₀-Hydrocarbyl stehen,

unter der Maßgabe, dass M2 und M3 nicht gleich sind.The monomers M2 and M3 preferably have the following structure:

wherein

R ⁹ and R ¹³

are the same or different and are H or C ₁ -C ₅₀ hydrocarbyl; and

R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ and R ¹⁶

are the same or different and are H or C ₁ -C ₁₀ -hydrocarbyl,

with the proviso that M2 and M3 are not the same.

In this case, when the copolymer contains both monomer M2 and M3 in copolymerized form, it is preferred that M2 and M3 differ by at least 6 carbon atoms, with M3 being particularly preferred as the longer-chain monomer. Accordingly, M3 in such a terpolymer most preferably contains at least 6 carbon atoms more than M2.

Preferably, R ⁹ and R ^{13 are} C ₈ -C ₄₈ -alkyl, particularly preferably C ₁₀ -C ₄₈ -alkyl, in particular C ₁₄ -C ₃₈ -alkyl, for example C ₁₆ -C ₂₈ -alkyl. Preferably R ⁹ and R ¹³ differ by at least 6 carbon atoms, it being preferred that R ¹³ is the longer chain, ie that R ^{13 contains} at least 6 more carbon atoms than R ⁹ .

R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different and are preferably C ₁ -C ₄ alkyl, and more preferably H or methyl. It is preferred that at least one and in particular at least two of the radicals R ¹⁰ , R ¹¹ or R ¹² in monomer M 2 or at least one and in particular at least two of the radicals R ¹⁴ , R ¹⁵ or R ¹⁶ in monomer M ³ stand for H. Specifically, all three radicals R ¹⁰ , R ¹¹ and R ¹² in monomer M2 or all three radicals R ¹⁴² , R ¹⁵ and R ¹⁶ in monomer M3 for H.

Accordingly, the monomers M2 and M3 are preferably longer-chain linear or branched alkenes, for example C ₆ -C ₅₀ -alkenes, preferably C ₁₀ -C ₅₀ -alkenes and in particular C ₁₂ -C ₅₀ -alkenes, for example C. ₁₂ -C ₄₀ -alkenes or C ₁₈ -C ₃₀ -alkenes. The double bond can be arranged both terminally (α-olefin) and internally (β-, γ-, δ-olefin, etc.). The alkenes may also be oligomers or polymers of alkenes, for example of C ₂ -C ₈ -alkenes, such as ethylene, propylene, 1- or 2-butene, isobutene, pentene, hexene or heptene, or in particular of C ₃ -C ₈ alkenes.

Preferably, the monomers M2 and M3 are alkenes having the C-C double bond in the α- or β-position (relative to the main chain of the molecule) and in particular in the α-position (terminal alkenes, α-alkenes).

The monomers M2 and M3 may also be alkene mixtures, for example mixtures obtained from industrial processes. This is the case in particular when the olefins used are olefin oligomers or polymers, such as polypropylene, polybutene or polyisobutene.

1. (a) einem Maleinsäuremonoester mit einem C₈-C₃₀-Alkohol, vorzugsweise mit einem C₁₀-C₂₆-Alkohol oder mit einem Gemisch solcher Alkohole, z.B. mit einem Gemisch aus C₁₆C₂₈-Alkoholen oder bevorzugt C₁₈-C₂₆-Alkoholen (Monomer M1),
2. (b) Maleinsäureanhydrid und
3. (c) einem C₈-C₃₀-Alken oder einem oder einem Gemisch solcher Alkene, z.B. einem Gemisch aus C₁₆-C₂₆-Alkenen oder bevorzugt aus C₂₀-C₂₄-Alkenen (Monomer M2).

With particular preference, the copolymer according to the invention is a copolymer

1. (A) a maleic acid monoester with a C ₈ -C ₃₀ -alcohol, preferably with a C ₁₀ -C ₂₆ -alcohol or with a mixture of such alcohols, eg with a mixture of C ₁₆ C ₂₈ -alcohols or preferably C ₁₈ -C ₂₆ Alcohols (monomer M1),
2. (b) maleic anhydride and
3. (C) a C ₈ -C ₃₀ alkene or one or a mixture of such alkenes, for example a mixture of C ₁₆ -C ₂₆ alkenes or preferably C ₂₀ -C ₂₄ alkenes (monomer M2).

1. (a) einem Maleinsäuremonoester mit einem C₈-C₃₀-Alkohol, vorzugsweise mit einem C₁₀-C₂₆-Alkohol oder mit einem Gemisch solcher Alkohole, z.B. mit einem Gemisch aus C₁₆C₂₈-Alkoholen oder bevorzugt C₁₈-C₂₆-Alkoholen (Monomer M1),
2. (b) Maleinsäureanhydrid,
3. (c) einem C₈-C₃₀-Alken (Monomer M2) und
4. (d) einem davon verschiedenen Alken (Monomer M3).

oder

• (c) einem C₈-C₃₀-Alken (Monomer M2) und
• (d) einem Alkengemisch, das dieses Alken nicht enthält und sich um wenigstens 6 Kohlenstoffatome davon unterscheidet (Monomer M3),

z.B. (c) einem C₁₀-C₁₄-Alken und (d) einem C₁₈-C₂₈-Alkengemisch oder einem C₃₀-C₅₀-Alkengemisch, z.B. einem C₃₅-C₄₅-Alkengemisch. Beispiele für solche Alkengemische sind Gemische wie sie aus Oligomerisierungs- oder Polymerisierungsprozessen von Alkenen, wie Ethylen, Propen, n-Buten oder Isobuten, entstehen, z.B. Polypropen, Polybuten oder insbesondere Polyisobuten mit einem M_n von z.B. 500, 550 oder 600.Alternatively, the copolymer according to the invention is particularly preferably a copolymer

1. (A) a maleic acid monoester with a C ₈ -C ₃₀ -alcohol, preferably with a C ₁₀ -C ₂₆ -alcohol or with a mixture of such alcohols, eg with a mixture of C ₁₆ C ₂₈ -alcohols or preferably C ₁₈ -C ₂₆ Alcohols (monomer M1),
2. (b) maleic anhydride,
3. (c) a C ₈ -C ₃₀ alkene (monomer M2) and
4. (d) a different alkene (monomer M3).

or

• (c) a C ₈ -C ₃₀ alkene (monomer M2) and
• (d) an alkene mixture which does not contain this alkene and differs by at least 6 carbon atoms (monomer M3),

for example (c) a C ₁₀ -C ₁₄ alkene and (d) a C ₁₈ -C ₂₈ alkene mixture or a C ₃₀ -C ₅₀ alkene mixture, for example a C ₃₅ -C ₄₅ alkene mixture. Examples of such alkene mixtures are mixtures such as those resulting from oligomerization or polymerization processes of alkenes, such as ethylene, propene, n-butene or isobutene, for example polypropene, polybutene or, in particular, polyisobutene having an M _n of, for example, 500, 550 or 600.

1. (a) einem Maleinsäurediester oder vorzugsweise Fumarsäurediester mit einem C₈-C₃₀-Alkohol, vorzugsweise mit einem C₁₀-C₂₆-Alkohol oder mit einem Gemisch solcher Alkohole, z.B. mit einem Gemisch aus C₁₆-C₂₈-Alkoholen oder bevorzugt C₁₈-C₂₆-Alkoholen (Monomer M1) und
2. (b) einem C₈-C₃₀-Alken oder einem oder einem Gemisch solcher Alkene, z.B. einem Gemisch aus C₁₆-C₂₆-Alkenen oder bevorzugt aus C₂₀-C₂₄-Alkenen (Monomer M2).

Alternatively, the copolymer according to the invention is particularly preferably a copolymer

1. (A) a maleic acid diester or preferably fumaric acid diester with a C ₈ -C ₃₀ -alcohol, preferably with a C ₁₀ -C ₂₆ -alcohol or with a mixture of such alcohols, eg with a mixture of C ₁₆ -C ₂₈ -alcohols or preferably C ₁₈ -C ₂₆ -alcohols (monomer M1) and
2. (b) a C ₈ -C ₃₀ alkene or one or a mixture of such alkenes, eg a mixture of C ₁₆ -C ₂₆ alkenes or preferably C ₂₀ -C ₂₄ alkenes (monomer M2).

1. (a) einem Maleinsäurediester oder vorzugsweise Fumarsäurediester mit einem C₈-C₃₀-Alkohol, vorzugsweise mit einem C₁₀-C₂₆-Alkohol oder mit einem Gemisch solcher Alkohole, z.B. mit einem Gemisch aus C₁₆-C₂₈-Alkoholen oder bevorzugt C₁₈-C₂₆-Alkoholen (Monomer M1),
2. (b) einem C₈-C₃₀-Alken (Monomer M2) und
3. (c) einem davon verschiedenen Alken (Monomer M3).

oder

• (b) einem C₈-C₃₀-Alken (Monomer M2) und
• (c) einem Alkengemisch, das dieses Alken nicht enthält und sich um wenigstens 6 Kohlenstoffatome davon unterscheidet (Monomer M3),

z.B. (c) einem C₁₀-C₁₄-Alken und (d) einem C₁₈-C₂₈-Alkengemisch oder einem C₃₀-C₅₀-Alkengemisch, z.B. einem C₃₅-C₄₅-Alkengemisch. Beispiele für solche Alkengemische sind Gemische wie sie aus Oligomerisierungs- oder Polymerisierungsprozessen von Alkenen, wie Ethylen, Propen, n-Buten oder Isobuten, entstehen, z.B. Polypropen, Polybuten oder insbesondere Polyisobuten mit einem M_n von z.B. 500, 550 oder 600.Alternatively, the copolymer according to the invention is particularly preferably a copolymer

1. (A) a maleic acid diester or preferably fumaric acid diester with a C ₈ -C ₃₀ -alcohol, preferably with a C ₁₀ -C ₂₆ -alcohol or with a mixture of such alcohols, eg with a mixture of C ₁₆ -C ₂₈ -alcohols or preferably C ₁₈ -C ₂₆ -alcohols (monomer M1),
2. (b) a C ₈ -C ₃₀ alkene (monomer M2) and
3. (c) a different alkene (monomer M3).

or

• (b) a C ₈ -C ₃₀ alkene (monomer M2) and
• (c) an alkene mixture which does not contain this alkene and differs by at least 6 carbon atoms (monomer M3),

for example (c) a C ₁₀ -C ₁₄ alkene and (d) a C ₁₈ -C ₂₈ alkene mixture or a C ₃₀ -C ₅₀ alkene mixture, for example a C ₃₅ -C ₄₅ alkene mixture. Examples of such alkene mixtures are mixtures such as those resulting from oligomerization or polymerization processes of alkenes, such as ethylene, propene, n-butene or isobutene, for example polypropene, polybutene or, in particular, polyisobutene having an M _n of, for example, 500, 550 or 600.

The copolymers used according to the invention are preferably obtainable by, preferably free-radical, polymerization, in particular solution polymerization, of the monomers M1, M2, optionally M3 and optionally M4.

• Didecanoylperoxid, 2,5-Dimethyl-2,5-di(2-ethylhexanoylperoxy)hexan, tert-Amylperoxy-2-ethylhexanoat, Dibenzoylperoxid, tert-Butylperoxy-2-ethylhexanoat, tert-Butylperoxydiethylacetat, tert-Butylperoxydiethylisobutyrat, 1,4-Di(tert-butylperoxycarbo)-cyclohexan als lsomerengemisch, tert-Butylperisononanoat, 1,1-Di-(tert-butylperoxy)-3,3,5-trimethylcyclohexan, 1,1-Di-(tert-butylperoxy)-cyclohexan, Methyl-isobutylketonperoxid, tert-Butylperoxyisopropylcarbonat, 2,2-Di-tert-butylperoxy)butan oder tert-Butylperoxacetat;
• tert-Butylperoxybenzoat, Di-tert-amylperoxid, Dicumylperoxid, die isomeren Di-(tert-butylperoxyisopropyl)benzole, 2,5-Dimethyl-2,5-di-tert-butylperoxyhexan, tert-Butylcumylperoxid, 2,5-Dimethyl-2,5-di(tert-butylperoxy)-hex-3-in, Di-tert-butylperoxid, 1,3-Diisopropylmonohydroperoxid, Cumolhydroperoxid oder tert-Butylhydroperoxid; oder dimere oder trimere Ketonperoxide, so wie sie z.B. aus der EP-A-0 813 550 bekannt sind

As starters for the radical polymerization, the usual radical initiators, such as organic peroxides, oxygen or azo compounds, can be used. Also mixtures of several radical starters are suitable. As free-radical initiators, it is possible, for example, to use one or more peroxides selected from the following commercially available substances:

• Didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxydiethyl isobutyrate, 1,4- Di (tert-butylperoxycarbo) cyclohexane as isomer mixture, tert-butyl perisononanoate, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di- (tert-butylperoxy) -cyclohexane, methyl isobutyl ketone peroxide, tert-butyl peroxy isopropyl carbonate, 2,2-di-tert-butylperoxy) butane or tert-butyl peroxyacetate;
• tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, the isomeric di- (tert-butylperoxyisopropyl) benzenes, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, tert-butylcumyl peroxide, 2,5-dimethyl-2 5-di (tert-butylperoxy) -hex-3-yne, di-tert-butyl peroxide, 1,3-diisopropyl monohydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide; or dimeric or trimeric ketone peroxides, such as those from the EP-A-0 813 550 are known

As peroxides, di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate, tert-amyl peroxypivalate or dibenzoyl peroxide or mixtures thereof are particularly suitable. As the azo compound, azobisisobutyronitrile ("AIBN") is exemplified. The free-radical initiators are metered in amounts customary for polymerizations.

In the preparation of the copolymer used according to the invention, it is also possible to use a precursor of the monomer M1 in the polymerization process and to carry out a functionalization reaction for the desired mono- or diester only after polymerization has taken place. Thus, for example, in the case where M1 is a maleic acid monoester, it is preferable to use maleic anhydride in the polymerization reaction and to convert this copolymerized monomer into the corresponding mono- or diester by reaction with the desired alcohol only in a conventional manner after polymerization has taken place , Such esterification reactions of polymerized maleic anhydride are known and, for example, in EP-A-0214786 which is incorporated herein by reference in its entirety. In this case, the esterification of the maleic anhydride is carried out so that a part of the anhydride used and copolymerized remains unchanged. It is also possible to use in the polymerization reaction instead of the actually desired monomers M1 the corresponding esters with shorter-chain alcohols, for example the methyl or ethyl esters of maleic acid or fumaric acid, and to convert these after polymerization by reaction with longer-chain alcohols in the desired ester.

The copolymers of the invention obtainable by the polymerization process are preferably composed essentially of the above-defined monomers M1, M2, optionally M3 and optionally M4. For manufacturing purposes, e.g. if maleic anhydride is used as a precursor for M1 or as monomer M4, it may contain, if appropriate, small amounts of maleic acid hydrolytically removed from the anhydride, e.g. caused by traces of water. The same applies when using other monomers M4. Low proportions means that the copolymer contains at most 2 mol%, preferably at most 1 mol%, more preferably at most 0.5 mol%, in particular at most 0.1%, of the acid, based on the other monomers. For reasons of manufacture, the copolymer may also contain minor amounts of other compounds, e.g. Regulator, included.

Preferably, the copolymers are used to lower the CP of fuel oils.

The copolymers according to the invention are used alone or in combination with other coadditives in amounts such that they have an effect as CP depressants in the additized fuel oil or lubricant.

Another object of the invention are the copolymers described above. With regard to preferred embodiments of these copolymers, reference is made to the above statements.

Fuel oil and lubricant compositions

Another object of the invention relates to fuel oil compositions containing a greater weight fraction of a boiling in the range of about 120-500 ° C middle distillate fuel and a smaller proportion by weight of at least one copolymer of the invention.

Another object of the invention relates to lubricant compositions containing a greater weight fraction of a conventional lubricant and a smaller weight fraction of at least one copolymer of the invention.

By fuel oils is meant according to the invention preferably fuels. Suitable fuels are gasolines and middle distillates, with middle distillates being preferred. Suitable middle distillates are, for example, diesel fuels, heating oil or kerosene, with diesel fuel and heating oil being particularly preferred.

The fuel oils are, for example, low-sulfur or high-sulfur petroleum refines or stone or lignite distillates, which usually have a boiling range of 150 to 400 ° C. The fuel oils may be standard fuel oil according to DIN 51603-1, which has a sulfur content of 0.005 to 0.2 wt .-%, or it is low sulfur fuel oils having a sulfur content of 0 to 0.005 wt. As examples for heating oil is in particular heating oil for domestic oil firing systems or heating oil called EL. The quality requirements for such heating oils are specified, for example, in DIN 51603-1 (cf also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A12, pp. 617 et seq., To which reference is expressly made).

The diesel fuels are, for example, petroleum raffinates, which usually have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or even beyond. However, these may also be so-called "ultra low sulfur diesel" or "city diesel", characterized by a 95% point of, for example, a maximum of 345 ° C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of, for example 285 ° C and a maximum sulfur content of 0.001 wt .-%. In addition to refining, diesel fuels are those produced by coal gasification or gas liquefaction (GTL) or biomass liquefaction (biomass to liquid). (BTL) fuels) are available. Also suitable are mixtures of the abovementioned diesel fuels with regenerative fuels, such as biodiesel.

The additive according to the invention is particularly preferred for the addition of low-sulfur diesel fuels, that is to say having a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight. % and especially less than 0.001% by weight of sulfur or for the addition of heating oil with a low sulfur content, for example with a sulfur content of at most 0.2% by weight, preferably of at most 0.05% by weight, more preferably of at most 0.005 Gew., Used.

Such fuel oil compositions may further comprise as fuel component biodiesel (from animal and / or vegetable production) in proportions of 0-30% by weight.

Preferred fuel oils are selected from diesel fuels, kerosene and fuel oil, which diesel fuel may be obtainable by refining, coal gasification, gas liquefaction or biomass liquefaction, may be a mixture of such products and optionally mixed with regenerative fuels. Such fuel oil compositions are preferred in which the sulfur content of the mixture is at most 500 ppm.

The copolymer of the present invention is preferably used in a proportion based on the total amount of the fuel oil composition, which in itself has a substantially sufficient influence on the CP value of the fuel oil compositions. Preferably, the additive is added in an amount of from 0.001 to 1% by weight, more preferably from 0.005 to 0.1% by weight, and especially from 0.01 to 0.05% by weight, based on the total amount of the fuel oil composition, used.

In the context of the present invention, the copolymers according to the invention can be used in combination with other conventional cold flow improvers and / or further lubricating and fuel oil additives.

Co-additives

The copolymers according to the invention can be added to the fuel oil compositions individually or as a mixture of such copolymers and optionally in combination with other additives known per se.

Suitable additives which may be included in the fuel oil compositions of this invention besides the copolymer of the present invention, especially for diesel fuels and fuel oils, include detergents, corrosion inhibitors, dehazers, demulsifiers, antifoams, antioxidants, metal deactivators, multifunctional stabilizers, cetane improvers, combustion improvers, dyes, Markers, solubilizers, antistatic agents, lubricity improvers, and other additives which improve the cold properties of the fuel, such as nucleators, flow improvers ("MDFI"), paraffin dispersants ("WASA") and the combination of the last two additives ("WAFI") (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A16, p.719 ff; or the patents cited at the outset for flow improvers).

1. a) Copolymere von Ethylen mit wenigstens einem weiteren ethylenisch ungesättigten Monomer;
2. b) Kammpolymere, die von den erfindungsgemäßen Copolymeren verschieden sind;
3. c) Polyoxyalkylene;
4. d) polare Stickstoffverbindungen;
5. e) Sulfocarbonsäuren oder Sulfonsäuren oder deren Derivate; und
6. f) Poly(meth)acrylsäureester.

Other conventional cold flow improvers which may be mentioned in particular are:

1. a) copolymers of ethylene with at least one further ethylenically unsaturated monomer;
2. b) comb polymers which are different from the copolymers according to the invention;
3. c) polyoxyalkylenes;
4. d) polar nitrogen compounds;
5. e) sulfocarboxylic acids or sulfonic acids or their derivatives; and
6. f) poly (meth) acrylic esters.

In the copolymers of ethylene with at least one further ethylenically unsaturated monomer a), the monomer is preferably selected from alkenylcarboxylic esters, (meth) acrylic esters and olefins.

Suitable olefins are, for example, those having 3 to 10 carbon atoms and having 1 to 3, preferably 1 or 2, in particular having one, carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally (α-olefins) and internally. However, preferred are α-olefins, more preferably α-olefins having 3 to 6 carbon atoms, such as propene, 1-butene, 1-pentene and 1-hexene.

Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C ₁ -C ₁₀ -alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, Heptanol, octanol, 2-ethylhexanol, nonanol and decanol.

Suitable alkenylcarboxylic esters are, for example, the vinyl and propenyl esters of carboxylic acids having 2 to 20 carbon atoms, the hydrocarbon radical of which is linear or can be branched. Preferred among these are the vinyl esters. Among the carboxylic acids with a branched hydrocarbon radical, preference is given to those whose branching is in the α-position to the carboxyl group, the α-carbon atom being particularly preferably tertiary, ie the carboxylic acid being a so-called neocarboxylic acid. Preferably, however, the hydrocarbon radical of the carboxylic acid is linear.

Examples of suitable alkenylcarboxylic esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, with vinyl esters being preferred. A particularly preferred alkenyl carboxylic acid ester is vinyl acetate.

Particularly preferably, the ethylenically unsaturated monomer is selected from alkenylcarboxylic esters.

Also suitable are copolymers which contain two or more mutually different alkenylcarboxylic acid esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenylcarboxylic ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.

The ethylenically unsaturated monomer is copolymerized in the copolymer in an amount of preferably from 1 to 50 mol%, particularly preferably from 10 to 50 mol% and in particular from 5 to 20 mol%, based on the total copolymer.

The copolymer a) preferably has a number-average molecular weight M _{n of} from 1,000 to 20,000, more preferably from 1,000 to 10,000 and in particular from 1,000 to 6,000.

worin
D für R¹⁷, COOR¹⁷, OCOR¹⁷, R¹⁸, OCOR¹⁷ oder OR¹⁷ steht,
E für H, CH₃, D oder R¹⁸ steht,
G für H oder D steht,
J für H, R¹⁸, R¹⁸COOR^17, Aryl oder Heterocyclyl steht,
K für H, COOR¹⁸, OCOR¹⁸, OR¹⁸ oder COOH steht,
L für H, R¹⁸ COOR¹⁸, OCOR¹⁸, COOH oder Aryl steht,
wobei
R¹⁷ für einen Kohlenwasserstoffrest mit wenigstens 10 Kohlenstoffatomen, vorzugsweise mit 10 bis 30 Kohlenstoffatomen, steht,
R¹⁸ für einen Kohlenwasserstoffrest mit wenigstens einem Kohlenstoffatom, vorzugsweise mit 1 bis 30 Kohlenstoffatomen, steht,
m für einen Molenbruch im Bereich von 1,0 bis 0,4 steht und
n für einen Molenbruch im Bereich von 0 bis 0,6 steht.Comb polymers b) are for example those described in " Comb-like polymers. Structure and Properties ", NA Platé and VP Shibaev, J. Poly. Sci. Macromolecular Revs., 8, pp. 117-253 (1974) are described. Of the described there, for example, comb polymers of the formula II are suitable

wherein
D is R ¹⁷ , COOR ¹⁷ , OCOR ¹⁷ , R ¹⁸ , OCOR ¹⁷ or OR ¹⁷ ,
E is H, CH ₃ , D or R ¹⁸ ,
G is H or D,
J is H, R ¹⁸ , R ¹⁸ COOR ^17, aryl or heterocyclyl,
K is H, COOR ¹⁸ , OCOR ¹⁸ , OR ¹⁸ or COOH,
L is H, R ¹⁸ COOR ¹⁸ , OCOR ¹⁸ , COOH or aryl,
in which
R ^{17 is} a hydrocarbon radical having at least 10 carbon atoms, preferably having 10 to 30 carbon atoms,
R ^{18 is} a hydrocarbon radical having at least one carbon atom, preferably having 1 to 30 carbon atoms,
m for a mole fraction in the range of 1.0 to 0.4 and
n represents a mole fraction in the range of 0 to 0.6.

Preferred comb polymers are obtainable, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an α-olefin or an unsaturated ester, such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol of at least 10 carbon atoms. Other preferred comb polymers are copolymers of α-olefins and esterified comonomers, for example, esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Also mixtures of comb polymers are suitable. Comb polymers may also be polyfumarates or polymaleinates. In addition, homopolymers and copolymers of vinyl ethers are suitable comb polymers.

Suitable polyoxyalkylenes c) are, for example, polyoxyalkylene esters, ethers, - ester / ethers and mixtures thereof. The polyoxyalkylene compounds preferably contain at least one, particularly preferably at least two, linear alkyl groups having from 10 to 30 carbon atoms and a polyoxyalkylene group having a molecular weight of up to 5,000. The alkyl group of the polyoxyalkylene radical preferably contains from 1 to 4 carbon atoms. Such polyoxyalkylene compounds are for example in the EP-A-0 061 895 as well as in the US 4,491,455 which is incorporated herein by reference in its entirety. Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III

R ¹⁹ [O- (CH ₂ ) _y ] _x OR ²⁰ (III)

wherein
R ¹⁹ and R ^{20 are} each independently R ²¹ , R ^{21 is} -CO-, R ^{21 is} -O-CO (CH ₂ ) _z - or
R ^{21 is} -O-CO (CH ₂ ) _z -CO-, where R ^{21 is} linear C ₁ -C ₃₀ -alkyl,
y is a number from 1 to 4,
x is a number from 2 to 200, and
z is a number from 1 to 4.

Preferred polyoxyalkylene compounds of the formula III in which both R ¹⁹ and R ^{20 are} R ²¹ are polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5,000. Preferred polyoxyalkylenes of the formula III in which one of the radicals R ^{19 is} R ²¹ and the other is R ²¹ -CO- are polyoxyalkylene esters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid. Preferred polyoxyalkylene compounds in which both R ¹⁹ and R ^{20 are} R ²¹ -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.

The polar nitrogen compounds d), suitably oil-soluble, may be both ionic and non-ionic and preferably have at least one, more preferably at least 2, substituents of the formula> NR ²² , wherein R ^{22 is} a C ₈ -C ₄₀ hydrocarbon radical. The nitrogen substituents may also be quaternized, that is in cationic form. An example of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof. The amines preferably contain at least one linear C ₈ -C ₄₀ -alkyl radical. Examples of suitable primary amines are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs. Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine. Also suitable are amine mixtures, in particular industrially available amine mixtures, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Amines, aliphatic". Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals.

Another example of polar nitrogen compounds are ring systems bearing at least two substituents of the formula -A-NR ²³ R ²⁴ wherein A is a linear or branched aliphatic hydrocarbon group optionally substituted by one or more groups selected from O, S , NR ³⁵ and CO, is interrupted, and R ²³ and R ^{24 are} a C ₉ -C ₄₀ hydrocarbon radical, optionally by one or more groups selected from O, S, NR ³⁵ and CO, interrupted and / or substituted by one or more substituents selected from OH, SH and NR ³⁵ R ³⁶ , wherein R ^{35 is} C ₁ C ₄₀ alkyl optionally interrupted by one or more groupings selected from CO, NR ³⁵ , O and S, and / or by one or more radicals selected from NR ³⁷ R ³⁸ , OR ³⁷ , SR ³⁷ , COR ³⁷ , COOR ³⁷ , CONR ³⁷ R38, aryl or heterocyclyl, wherein R ³⁷ and R ^{38 are} each independently selected from H or C ₁ -C ₄ alkyl; and R ^{36 is} H or R ³⁵ .

Preferably, A is a methylene or polymethylene group having 2 to 20 methylene units. Examples of suitable radicals R ²³ and R ²⁴ are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. The cyclic system can be either homocyclic, heterocyclic, condensed polycyclic or non-condensed polycyclic systems. Preferably, the ring system is carbo- or heteroaromatic, in particular carboaromatic. Examples of such polycyclic ring systems are condensed benzoic structures, such as naphthalene, anthracene, phenanthrene and pyrene, condensed non-benzoidic structures, such as azulene, indene, hydrindene and fluorene, uncondensed polycycles, such as diphenyl, heterocycles, such as quinoline, indole, dihydroindole, benzofuran, Coumarin, isocoumarin, benzthiophene, carbazole, diphenylene oxide and diphenylene sulfide, non-aromatic or partially saturated ring systems such as decalin, and three-dimensional structures such as α-pinene, camphene, bornylene, norborane, norbornene, bicyclooctane and bicyclooctene.

Another example of suitable polar nitrogen compounds are condensates of long-chain primary or secondary amines with carboxyl group-containing polymers.

The polar nitrogen compounds mentioned here are in the WO 00/44857 and in the references cited therein, which is hereby incorporated by reference in its entirety.

Suitable polar nitrogen compounds are also in the DE-A-198 48 621 of the DE-A-196 22 052 or the EP-B-398 101 described, to which reference is hereby made.

worin
Y für SO₃ ^-(NR²⁵ ₃R²⁶)⁺, SO₃ ^-(NHR²⁵ ₂R²⁶)⁺, SO₃ ^-(NH₂R²⁵R²⁶), SO₃ ^-(NH₃R²⁶) oder
SO₂NR²⁵R²⁶ steht,
X für Y, CONR²⁵R²⁷, CO₂ ^-(NR²⁵ ₃R²⁷)⁺, CO₂ ^-(NHR²⁵ ₂R²⁷)⁺, R²⁸-COOR²⁷, NR²⁵COR²⁷, R²⁸OR²⁷, R²⁸OCOR²⁷, R²⁸R²⁷, N(COR²⁵)R²⁷ oder Z^-(NR²⁵ ₃R²⁷)⁺ steht,
wobei
R²⁵ für einen Kohlenwasserstoffrest steht,
R²⁶ und R²⁷ für Alkyl, Alkoxyalkyl oder Polyalkoxyalkyl mit wenigstens 10 Kohlenstoffatomen in der Hauptkette stehen,
R²⁸ für C₂-C₅-Alkylen steht,
Z^- für ein Anionenäquivalent steht und
A und B für Alkyl, Alkenyl oder zwei substituierte Kohlenwasserstoffreste stehen oder gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, ein aromatisches oder cycloaliphatisches Ringsystem bilden.Suitable sulfocarboxylic acids / sulfonic acids or their derivatives e) are, for example, those of the general formula IV

wherein
Y is SO ₃ ^- (NR ²⁵ ₃ R ²⁶ ) ⁺ , SO ₃ ^- (NHR ²⁵ ₂ R ²⁶ ) ⁺ , SO ₃ ^- (NH ₂ R ²⁵ R ²⁶ ), SO ₃ ^- (NH ₃ R ²⁶ ) or
SO ₂ NR ²⁵ R ²⁶ ,
X for Y, CONR ²⁵ R ²⁷ , CO ₂ ^- (NR ²⁵ ₃ R ²⁷ ) ⁺ , CO ₂ ^- (NHR ²⁵ ₂ R ²⁷ ) ⁺ , R ²⁸ -COOR ²⁷ , NR ²⁵ COR ²⁷ , R ²⁸ OR ²⁷ , R ²⁸ OCOR ²⁷ , R ²⁸ R ²⁷ , N (COR ²⁵ ) R ²⁷ or Z ^- (NR ²⁵ ₃ R ²⁷ ) ⁺ ,
in which
R ^{25 is} a hydrocarbon radical,
R ²⁶ and R ^{27 are} alkyl, alkoxyalkyl or polyalkoxyalkyl having at least 10 carbon atoms in the main chain,
R ^{28 is} C ₂ -C ₅ -alkylene,
Z ^{- stands} for an anion equivalent and
A and B are alkyl, alkenyl or two substituted hydrocarbon radicals or together with the carbon atoms to which they are attached form an aromatic or cycloaliphatic ring system.

Such sulfocarboxylic acids or sulfonic acids and their derivatives are in the EP-A-0 261 957 which is incorporated herein by reference in its entirety.

Suitable poly (meth) acrylic esters f) are both homo- and copolymers of acrylic and methacrylic acid esters. Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight average molecular weight of the polymer is preferably from 50000 to 500000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic esters of saturated C ₁₄ - and C ₁₅ alcohols, wherein the acid groups are neutralized with hydrogenated tallow amine. Suitable poly (meth) acrylic esters are, for example, in WO 00/44857 which is incorporated herein by reference in its entirety.

In addition to the copolymers of the invention, the fuel oil composition according to the invention preferably comprises at least one of the abovementioned conventional cold flow improvers and in particular at least one of the calf flow improvers the group a). These cold flow improvers are used in particular for lowering the CFPP value of fuel oil compositions additized therewith.

additive packages

Finally, the subject of the present application is an additive package comprising at least one copolymer according to the invention and at least one further additive, preferably selected from the above co-additives and optionally at least one diluent.

Preferably, the additive package contains at least one of the aforementioned conventional cold flow improvers, and more particularly at least one of the cold flow improvers of group a).

Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or bright stock. Also suitable are aromatic and aliphatic hydrocarbons and alkoxyalkanols. When middle distillates, especially in diesel fuels and heating oils preferably used diluents are naphtha, kerosene, diesel fuels, aromatic hydrocarbons such as Solvent Naphtha heavy, Solvesso ^® or Shellsol ^®, as well as mixtures of these solvents and diluents.

The copolymer according to the invention is preferably present in the additive packages in an amount of from 0.1 to 99% by weight, more preferably from 1 to 90% by weight and in particular from 10 to 80% by weight, based on the total weight of the additive package, in front.

The copolymers of the invention show improved performance compared to conventional cold flow improvers. In particular, they lower the CP value of fuel oils additized therewith more effectively than comparable additives of the prior art. Another advantage is that they have no negative impact on other additives contained in fuel oils, especially on cold flow improvers and especially on those that are intended to lower the CFPP value.

The invention will now be explained in more detail with reference to the following nonlimiting examples.

1. Production examples

A total of four different copolymers of the invention were prepared by solution polymerization.

Copolymer 1

In a 2L stirred tank, an α-C ₂₀ -C ₂₄ olefin (392 g) was added and heated to 150 ° C with stirring under a nitrogen atmosphere. This was then added with maleic anhydride (130 g) together with di-tert-butyl peroxide (5 g) over 5 h. After one hour reaction time, o-xylene (1040 g), p-toluenesulfonic acid (0.2 g) and decanol (231 g) were added and the reaction mixture was reacted at 150 ° C for 4 h.
Solids content: 46.8%; K value: 13.1

Copolymer 2

In a stirred tank, an α-C ₂₀ -C ₂₄ olefin (235 g) was added and heated to 150 ° C with stirring under a nitrogen atmosphere. This was then added with maleic anhydride (78 g) along with di-tert-butyl peroxide (3.1 g) over 5 h. After one hour of reaction time, o-xylene (1250 g), p-toluenesulfonic acid (0.1 g) and stearyl alcohol (237 g) melted at 70 ° C were added and the reaction mixture was reacted at 150 ° C for 4 hours. After completion of the reaction, o-xylene was removed under reduced pressure.
Solids content: 98.9%; K value: 9.9

Copolymer 3

In a stirred tank, an α-C ₂₀ -C ₂₄ olefin (178 g) and an α-C ₁₂ olefin (152 g) were added and heated to 150 ° C with stirring under a nitrogen atmosphere. These were then added with maleic anhydride (148 g) together with di-tert-butyl peroxide (24 g) over 6 h. After one hour of reaction time, o-xylene (980 g), p-toluenesulfonic acid (0.12 g) and Nafol 20+ molten at 70 ° C (a fatty alcohol mixture with chain lengths greater than 20 carbon atoms) (317 g) were added and the reaction mixture was reacted at 150 ° C for 4 h.
Solids content: 54.1%; K value: 11.3

Copolymer 4

In a stirred tank, an α-C ₁₂ olefin (170 g) and PIB 550 (molecular weight 550 polyisobutene) were added and heated to 150 ° C with stirring under a nitrogen atmosphere. These were then added with maleic anhydride (125 g) together with di-tert-butyl peroxide (4.2 g) over 6 h. After one hour reaction time, o-xylene (850 g), p-toluenesulfonic acid (0.1 g) and molten Nafol 20+ (a fatty alcohol mixture with chain lengths greater than 20 C atoms) (512 g) were added at 70 ° C and the reaction mixture was reacted at 150 ° C for 4 h. After completion of the reaction, o-xylene was removed under reduced pressure.
Solids content: 98.9%; K value: 10.5

The content of the individual comonomers was determined by IR spectroscopy. To determine the molar masses, the K value was determined.
Determination of the K value (relative viscosity)

The procedure was carried out in a Ubbelohde viscometer from Schott, type 501 10 / I (three-legged). The solvent used was Solvesso 150. A 1% polymer solution was used.

In a 100 ml volumetric flask, a 1% polymer solution was prepared and stirred for at least 1 h. The solution was introduced through a paper filter into a Ubbelohde Type I viscometer and measured 3 times at 25 ° C in a water bath. The cycle time [s] between the upper and the lower mark was determined. Previously, the kinematic viscosity of the solvent had been determined. Table 1: Analytical data of the polymers obtained Polymer Ex. No. M1 + M4 [mol%] M2 [mol%] M3 [mol%] K value 1 50 50 - 13.1 2 50 50 - 9.9 3 50 30 20 11.3 4 50 40 10 10.5

2. Application examples

With the above-prepared copolymers 1 to 4, the following experiments were carried out. Polymer solutions in xylene were prepared for this purpose (polymer solution 1: 47% by weight of polymer 1, polymer solution 2: 99% by weight of polymer 2, polymer solution 3: 54% by weight of polymer 3, polymer solution 4: 99% by weight of polymer 4 ).

Conventional middle distillate fuels were additized with the above copolymers according to the invention in different metering rates and the CP value was determined.

The Cloud Point (CP) was determined according to ASTM D 2500 and the Cold Filter Plugging Point (CFPP) according to DIN EN116.

1. a) Heizöl 1 (HÖ1): CP = 2,9 °C, CFPP = 2 °C, d₁₅ = 856 kg/m³, IBP (initial boiling point) = 186 °C, FBP (final boiling point) = 376 °C, 90-20 (Temperaturdifferenz des 90 Vol.-%- und 20 Vol.-%-Wertes der Siedekurve) = 115 °C, 20,9 % n-Paraffine
2. b) Heizöl 2 (HÖ2): CP = 0,1 °C, CFPP = -5 °C, d₁₅ = 833 kg/m³, IBP = 176 °C, FBP = 368 °C, 90-20 = 119 °C, 29,6 % n-Paraffine
3. c) Heizöl 3 (HÖ3): CP = 3,0 °C, CFPP = 1 °C, d₁₅ = 854 kg/m³, IBP = 186 °C, FBP = 374 °C, 90-20 = 119 °C, 22,2 % n-Paraffine
4. d) Dieselkraftstoff 1 (DK1): CP = -7 °C, CFPP = -8 °C, d₁₅ = 832 kg/m³, IBP = 170 °C, FBP = 357 °C, 90-20 = 118 °C, 22,1 % n-Paraffine
5. e) Dieselkraftstoff 2 (DK2): CP = -7,2 °C, CFPP = -8 °C, d₁₅ = 831 kg/m³, IBP = 185 °C, FBP = 352 °C, 90-20 = 103 °C, 25,5 % n-Paraffine

Used middle distillates:

1. a) Heating oil 1 (HÖ1): CP = 2.9 ° C, CFPP = 2 ° C, d ₁₅ = 856 kg / m ³ , IBP (initial boiling point) = 186 ° C, FBP (final boiling point) = 376 ° C, 90-20 (temperature difference of the 90 vol.% And 20 vol.% Of the boiling curve) = 115 ° C, 20.9% n-paraffins
2. b) Fuel oil 2 (HÖ2): CP = 0.1 ° C, CFPP = -5 ° C, d ₁₅ = 833 kg / m ³ , IBP = 176 ° C, FBP = 368 ° C, 90-20 = 119 ° C, 29.6% n-paraffins
3. c) Fuel oil 3 (HÖ3): CP = 3.0 ° C, CFPP = 1 ° C, d ₁₅ = 854 kg / m ³ , IBP = 186 ° C, FBP = 374 ° C, 90-20 = 119 ° C , 22.2% n-paraffins
4. d) 1 diesel fuel (DK1): CP = -7 ° C, CFPP = -8 ° C, d ₁₅ = 832 kg / m ^3, IBP = 170 ° C, FBP = 357 ° C, 90-20 = 118 ° C , 22.1% n-paraffins
5. e) diesel fuel 2 (DK2): CP = -7.2 ° C, CFPP = -8 ° C, d ₁₅ = 831 kg / m ^3, IBP = 185 ° C, FBP = 352 ° C, 90-20 = 103 ° C, 25.5% n-paraffins

The determined CP values (in ° C) of the additized middle distillate fuels are listed in Tables 2 and 3. Table 2: CP of additized fuel oils copolymer Dosing rate [ppm] CP [° C] (HÖ1) Dosing rate [ppm] CP [° C] (HÖ2) Dosing rate [ppm] CP [° C] (HÖ3) - - 2.9 - 0.1 - 3 1 100 2.6 100 -0.1 500 2.4 500 -0.8 2 100 2.6 100 -0.7 100 2.1 500 1.8 500 -0.7 500 1.4 3 100 2.2 100 -0.8 100 1.9 500 1.7 500 -1.3 500 1.3 4 100 2.4 100 -0.6 500 2.0 500 -0.9 500 1.8 copolymer Dosing rate [ppm] CP [° C] (DK1) Dosing rate [ppm] CP [° C] (DK2) - - -7 - -7.2 1 100 -9 100 -8.3 500 -9.2 500 -8.9 2 100 -7.7 100 -7.6 500 -7.6 500 -7.6 3 100 -8.5 100 -8.2 500 -8.6 500 -8.3 4 100 -8.3 100 -8.2 500 -8.8 500 -8.4

Claims (21)

Use of a copolymer which is made up of monomers comprising M1, M2, optionally M3 and optionally M4, where M1 has the following general structure:

wherein R ¹ and R ^{2 are} H, C ₁ -C ₄ -hydrocarbyl or -COOR ⁵ , where one of the radicals R ¹ or R ^{2 is} H or C ₁ -C ₄ -hydrocarbyl and the other radical is -COOR ⁵ ; R ³ and R ^{4 are} H, C ₁ -C ₄ -hydrocarbyl or -COOR ⁶ , where one of the radicals R ³ or R ^{4 is} H or C ₁ -C ₄ -hydrocarbyl and the other radical is -COOR ⁶ ; R ^{5 is} H or C ₁ -C ₄₀ hydrocarbyl; and R ^{6 is} C ₁ -C ₄₀ hydrocarbyl; and M2 and M3 are different ethylenically unsaturated C ₂ -C ₅₀ hydrocarbons; and
M4 has the following general structure:

wherein
R ⁷ and R ^{8 are} independently H or C ₁ -C ₄ hydrocarbyl,
for lowering the CP value of fuel oils and lubricants. Use according to claim 1, wherein the copolymer contains the monomers M1, M2, optionally M3 and optionally M4 in copolymerized form. Use according to one of the preceding claims, wherein the monomers M1, M2, M3 and M4 are present in the copolymer in the following molar proportions: M1 + M4: 0.1 to 0.7 M2: 0.05 to 0.7 M3: 0 to 0.7, wherein M1 and M4 are contained in a molar ratio of 1: 0 to 1: 1; and
wherein the sum of the molar proportions of M2 and M3 is 0.3 to 0.9. Use according to one of the preceding claims, wherein in the monomer M1 R ¹ and R ^{3 are} H, R ^{2 is} -COOR ⁵ and R ^{4 is} -COOR ⁶ . Use according to claim 4, wherein R ^{5 is} H and R ^{6 is} C ₁ -C ₄₀ hydrocarbyl. Use according to one of claims 4 or 5, wherein the monomer M1 is a maleic acid monoester derived from C ₆ -C ₄₀ alcohols. Use according to one of claims 5 or 6, wherein the copolymer is made up of monomers comprising M1, M2, M4 and optionally M3. Use according to claim 7, wherein the copolymer contains the monomers M1 and M4 in copolymerized form in a molar ratio of 20: 1 to 1: 1. Use according to any one of claims 1 to 3, wherein in the monomer M1 R ^{1 is} -COOR ⁵ and R ^{4 is} -COOR ⁶ . Use according to claim 9, wherein R ^{5 is} C ₁ -C ₄₀ hydrocarbyl. Use according to one of the preceding claims, wherein in the monomer M4 R ⁷ and R ⁸ stand for H. Use according to any one of the preceding claims, wherein the monomers M2 and M3 have the following general structures:

wherein
R ⁹ and R ^{13 are the} same or different and are H or C ₁ -C ₄₈ hydrocarbyl; and
R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ and R ^{16 are the} same or different and are H or C ₁ -C ₄ -hydrocarbyl,
with the proviso that M2 and M3 are not the same. Use according to claim 12, wherein
R ⁹ and R ^{13 are} C ₈ -C ₄₈ hydrocarbyl; and
R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ and R ^{16 are the} same or different and are H or methyl. Copolymer as defined in any one of the preceding claims. A fuel oil composition comprising a major weight fraction of a middle distillate fuel boiling in the range of 120-500 ° C and a minor proportion by weight of at least one copolymer as defined in any one of claims 1 to 14. A fuel oil composition according to claim 15, wherein the middle distillate fuel is selected from diesel fuels, kerosene and fuel oil. A fuel oil composition according to claim 16, wherein the diesel fuel is by refining, coal gasification, gas liquefaction or biomass liquefaction is available, is a mixture of such products and optionally mixed with regenerative fuels. A fuel oil composition according to any one of claims 15 to 17, wherein the sulfur content of the mixture is at most 500 ppm. A lubricant composition comprising a major proportion by weight of a conventional lubricant and a minor proportion by weight of at least one copolymer as defined in any one of claims 1 to 14. Use or composition according to any one of claims 1 to 13 or 15 to 19, wherein the copolymer is used in combination with at least one other conventional lubricant or fuel oil additive. An additive package comprising at least one copolymer as defined in any one of claims 1 to 14 in combination with at least one other conventional lubricant or fuel oil additive.