WO2018054892A1

WO2018054892A1 - Terpolymers of maleic anhydride, acrylates, and alpha-olefins, in particular for use as flow improvers for petroleum

Info

Publication number: WO2018054892A1
Application number: PCT/EP2017/073611
Authority: WO
Inventors: Ivette Garcia Castro; Stefan Frenzel; Maria Heuken; Edward Bohres
Original assignee: Basf Se
Priority date: 2016-09-21
Filing date: 2017-09-19
Publication date: 2018-03-29

Abstract

The invention relates to copolymers containing the monomer units (formula (A), (B), and (C)), in which R^a is hydrogen or methyl, R¹, R², R³ is either (i) short-chain, unbranched alkyl groups with 16 to 26 carbon atoms or (ii) short-chain unbranched or branched alkyl groups with 6 to 12 carbon atoms or cycloalkyl groups with 6 to 12 carbon atoms, wherein the sum of the monomer units (A), (B), and (C) is more than 50 mol.%, based on the total sum of all of the monomer units in the copolymer, and 20 mol.% to 40 mol.% of the monomer units (A), (B), and (C), based on the sum of all of the monomer units (A), (B), and (C) have groups R¹, R², R³ selected from the groups (ii). The invention additionally relates to a method for producing same and to the use thereof.

Description

Terpolymers of maleic anhydride, acrylates and alpha-olefins, especially for use as flow improvers for petroleum

description

The present invention relates to copolymers based on an alpha-olefin, an acrylic acid ester and a maleic anhydride, processes for their preparation and their use. Crude or mineral oils containing paraffinic waxes 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 (CP), 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 leads to the deterioration of the flow properties of the mineral oils and may, for example, lead to the adhesion of fuel filters both in tanks and in motor vehicles. Finally, at temperatures below the so-called "pour point" (PP), there is no flow, so-called flow improvers, which prevent or at least suppress the appearance of these crystals to a certain extent, are used to prevent this phenomenon are known in the art and often represent copolymers having a polyaddition backbone that often has differently functionalized side chains that allow the introduction of long or short chain hydrocarbon radicals.

The object of these flow improvers is therefore to improve the viscosity and reduce the pour point in the medium used, such as mineral oil. On the other hand, these flow improvers themselves must have the lowest possible pour point. The phenomenon described above is described, for example, in EP A 1 746 147 A1. Therein is described in general terms a copolymer which is made up of two to four monomers, wherein at least one monomer is a polycarboxylic acid ester and another monomer is an olefin. As specifically described copolymers, copolymers of an alpha-olefin having 20 to 40 carbon atoms and maleic anhydride are disclosed, whereby the anhydride ring is opened with decanol, stearyl alcohol or a fatty alcohol mixture having chain lengths of more than 20 carbon atoms. Another example relates to a terpolymer of two olefins with maleic anhydride wherein the anhydride ring is opened with a fatty alcohol mixture having chain lengths greater than 20 carbon atoms. WO 2014/095412 A1 describes polymeric compositions as pour point

Oppressors for crude oils or mineral oils of copolymers obtained by radical polymerization of monoethylenically unsaturated monomers in the presence of at least one ethylene Vinyl ester copolymers are formed. In this case, a mixture of alkyl acrylates is used as monoethylenically unsaturated monomers.

WO 2014/095408 A1 describes polymer formulations of copolymers of alkyl acrylates with ethylene-vinyl copolymers and two different solvents.

EP 1 857 529 A1 and EP 1 526 167 A2 describe cold flow improvers for fuel oils comprising a copolymer of ethylene and an acrylic or vinyl ester and a comb polymer.

EP 0 485 773 B1 describes flow improvers from conventional ethylene-based flow improvers and copolymers from the reaction of alkyl acrylates with dicarboxylic esters, their anhydrides and amines. Dicarboxylic acid monoamides as flow improvers are also described in EP 0 436 151 B1. Copolymers useful as fuel and lubricant additive as well as their reaction products with amines are also described in WO 95/07944 A1 and WO 95/07944 A1. Also for other purposes comparable copolymers are used. For example, EP 0 640 104 B1 describes the use of copolymers of vinyl alkyl ethers, dicarboxylic anhydrides and dicarboxylic acids in hairsprays.

Despite the known in the art copolymers as flow improvers, there is a need for new flow improvers that can better meet the above requirements for viscosity improvement and lowering the pour point and / or also have even a low pour point itself.

It is therefore an object of the present invention to provide, manufacture and use such improved flow improvers for the above purposes. The object is achieved by a copolymer containing the monomer units

(A) and (C) ^H ° (°) ^CC (°) ° ^R where

R ^{a is} hydrogen or methyl,

R ¹ , R ² , R ^{3 are} either (i) long-chain, unbranched alkyl radicals having 16 to 26 carbon atoms or (ii) short-chained, unbranched or branched alkyl radicals having 6 to 12 carbon atoms or cycloalkyl radicals having 6 to 12 carbon atoms, the sum of the monomer units (A), (B) and (C) based on the total sum of all monomer units in the copolymer is more than 50 mol% and wherein

20 mol% to 40 mol% of the monomer units (A), (B), (C) based on the sum of the monomer units (A), (B), (C) radicals R ¹ , R ² , R ³ which are selected from the radicals (ii).

The object is likewise achieved by a process for preparing a copolymer according to the invention comprising the steps

(a) free-radical polymerization of maleic anhydride (C) with a monomer of formula (Α ') R ¹ -CH = CH ₂ and a monomer of formula (Β') CH ₂ = C (R ^a ) C (O) OR ² and

(b) reacting the copolymer intermediate obtained in (a) with an alcohol R ³ -OH at least in part to ring-open maleic anhydride monomer present in the intermediate.

The object is also achieved by the use of a copolymer according to the invention as a pour point improver, paraffin inhibitor or viscosity reducer.

It has surprisingly been found that copolymers with a precisely defined proportion of long-chain side chains of hydrocarbon radicals have surprisingly good properties. The copolymer of the invention (also synonymously referred to herein as copolymer) is characterized in that the monomer units (A), (B) and (C) are contained. These monomer units (A), (B) and (C) together represent at least half of all monomer units in the copolymer. Accordingly, the sum of the monomer units (A), (B) and (C) is based on the sum of all monomer units in the copoly - Merisat more than 50 mol%. Preferably, the sum of the monomer units (A), (B) and (C) based on the total sum of all monomer units in the copolymer at least 60 mol%, more preferably at least 70 mol%, more preferably 75 mol% and more preferably at least 80 mol%. Preferably, the monomer units each occur in the same ratio to each other. Accordingly, the molar ratio (A) :( B) :( C) is preferably 1: 1: 1.

Accordingly, further monomer units which can not be assigned to the monomer units (A), (B) or (C) can occur in the copolymer. Accordingly, these other monomer units have no structure of the units (A), (B) or (C) and / or do not meet the corresponding definitions of the radicals R ^a , R ¹ , R ² , R ³ given herein. For the sake of clarity, it should be pointed out that different monomer units, which together fall under a structure of the units and in different ways satisfy the associated variable definitions for the corresponding unit, as a monomer unit are summarized. For example, apply two different monomer units, both of which have the structure (A) and differ in the definition of R ^1, but satisfy both definitions given herein for R ^1, such as a linear C16 and C18 radical, both are as the monomer unit (A) belonging. Likewise, it is clear to the person skilled in the art that the copolymer according to the invention typically represents a mixture of different polymer chains with different polymer chain length and varying monomer sequence.

The further monomer units which can not be assigned to the monomer units (A), (B) or (C) are specifically used or not used in a targeted manner. If monomeric units used in a targeted manner, a copolymer according to the invention should be obtained which contains more has three monomer units. This is the case in particular when more than three, for example four, five or six monomers corresponding to corresponding monomer units are used to form the copolymer according to the invention. Preferably, however, only three monomers are used selectively according to the invention. Here, a copolymer formed from such three selectively used monomers is referred to as a terpolymer. Nevertheless, monomeric units which are not used in a targeted manner are typically also present in such a terpolymer. This also applies to the copolymer of the invention. Non-specifically used monomer units typically result from minor constituents. These can occur as impurities of the educts, for example the monomers corresponding to the monomer units. Here are, for example, to mention monomers in which the radicals R ¹ , R ² , R ³ corresponding side chains have a higher or lower number of carbon atoms. Thus, for example, a monomer corresponding to the monomer unit (A) could be present which has an alkyl radical R ¹ of 27 carbon atoms. Likewise, it is possible, for example, that monomer units occur analogously to the monomer unit (C) which carry a hydrogen instead of the radical R ² . It is also possible that after the polymerization further derivatization takes place, which can also form by-products. Thus, for example, the monomer unit (C) can be formed from the corresponding anhydride monomer with subsequent ring opening. In this case, the corresponding dicarboxylic acid (R ³ = H) or a diester are possible as further possible by-products.

The monomer units (A), (B) and (C) each have a radical R ¹ , R ² and R ³ , each of which represents side chains of the Copolymerisatgerüstes. The monomer units (A), (B) and (C) may be distributed alternately, block by block (for example, two, three, four, five or more blocks) in any order or randomly in the copolymer.

The radicals R ¹ , R ² , R ³ are either (i) long-chain, unbranched alkyl radicals having 16 to 26 carbon atoms or (ii) short-chained, unbranched or branched alkyl radicals having 6 to 12 carbon atoms or cycloalkyl radicals having 6 to 12 carbon atoms. Here, the term "alkyl" stands for an acyclic, saturated hydrocarbon which may be unbranched or branched. Typical alkyl radicals are n-hexyl, n-heptyl, n-octyl, n-dodecyl, C18H37, C20H41, C22H45 "Cycloalkyl" for a cyclic, saturated hydrocarbon. An example of this is cyclohexyl.

The radicals R ¹ , R ² , R ³ are thus selected from a radical (i) which is long-chain and a short-chain radical (ii).

The long-chain radical (i) is selected from unbranched alkyl radicals having 16 to 26 carbon atoms. Accordingly, unbranched alkyl radicals may be selected which have 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 or 26 carbon atoms. Preferably, the long-chain radicals (ii) have unbranched alkyl radicals having 18 to 24, ie 18, 19, 20, 21, 22, 23 or 24 carbon atoms, further preferred radicals having 18, 20 or 22 carbon atoms.

The short-chain radical (ii) is selected from straight or branched alkyl radicals having 6 to 12 carbon atoms or cycloalkyl radicals having 6 to 12 carbon atoms. Accordingly, the short-chain radical (ii) may have 6, 7, 8, 9, 10, 11 or 12 carbon atoms. Preferably, the radical (ii) has 6 to 10, ie 6, 7, 8, 9 or 10 carbon atoms. Preferably, the radical (ii) has 6, 8 or 12 carbon atoms. The short-chain radical (ii) can be selected from both the alkyl and the cycloalkyl radicals or only one of the radicals, either alkyl radical or cycloalkyl radical. Thus, in one embodiment, the short-chain radical (ii) has cycloalkyl radicals, while in an alternative embodiment, the short-chain radical (ii) has no cycloalkyl radicals, unless both radicals are selected. Should the short-chain radical (ii) have cycloalkyl radicals, this is selected by cycloalkyl radicals having 6 to 12 carbon atoms. If the short-chain radical (ii) has no cycloalkyl radicals, this is selected from unbranched or branched alkyl radicals having 6 to 12 carbon atoms.

Based on the sum of the monomer units (A), (B), (C) have 20 mol% to 40 mol% of the monomer units (A), (B), (C) radicals R ¹ , R ² , R ³ which are selected from the radicals (ii). Accordingly, 20 mol% to 40 mol% of the monomer units (A), (B), (C) are short-chain, ie selected from unbranched or branched alkyl radicals or cycloalkyl radicals having 6 to 12 carbon atoms, preferably 6 to 10, preferably 6, 8 or 12, carbon atoms.

It is preferable that 30 mol% to 35 mol%, more preferably 32 mol% to 34 mol%, more preferably 33 mol%, of the monomer units (A), (B), (C) based on the Total of the monomer units (A), (B), (C) radicals R ¹ , R ² , R ³ , which are selected from the radicals (ii). Accordingly, the long-chain fraction, namely the fraction which has radicals (i), 80 mol% to 60 mol%, preferably 70 mol% to 65 mol%, more preferably 68 mol% to 66 mol%, further more preferably 67 mol%.

In principle, it is possible that each radical R ¹ , R ² , R ³ can carry both long-chain and short-chain radicals, as long as the entire short-chain fraction has the abovementioned values. It is also not necessary for the short chain radicals to be uniformly distributed. Thus, it is possible, for example, for all radicals R ¹ , R ² , R ³ to occur equally frequently in the polymer and for 1/3 of all radicals R ¹ , R ² and R ^{3 to be} short-chained and the remaining (2/3 R ¹ , 2 / 3 R ² , 2/3 R ³ ) must be correspondingly long-chain, so that the sum of all short-chain monomer units (A), (B), (C) also yields a total of 1/3 (= 33 mol%). Likewise, it is possible, for example, that in each case half of the radicals R ¹ and R ² or in each case half of the radicals R ¹ and R ³ or in each case half of the radicals R ² and R ^{3 are} short-chain and the remaining (50% R ¹ , 50% R ² , 100% R ³ or 50% R ¹ , 100% R ² , 50% R ³ or 100% R ¹ , 50% R ² , 100% R ³ ) must be correspondingly long-chain, so that the sum of all short-chain monomer units (A), (B), (C) also gives a total of 1/3 (= 33 mol%). It is likewise possible, for example, for only the radical R ¹ or only the radical R ² or only the radical R ^{3 to be} exclusively short-chained and the others (0% R ¹ , 100% R ² , 100% R ³ or 100% R ¹ , 0% R ² , 100% R ³ or 100% R ¹ , 100% R ² , 0% R ³ ) must be long-chain, so that the sum of all short-chain monomer units (A), (B), (C) also a total of 1/3 (= 33 mol%). However, it is also possible, for example, an uneven distribution in which 3/12 R ¹ , 7/12 R ² and 2/12 R ^{3 are} short-chained.

It is preferred that, based on the sum of all radicals R ¹ , R ² , R ³ , selected from radicals (ii), more than 50 mol% (more preferably more than 60 mol%, more preferably more than 70 mol%, more preferably more than 80 mol%, more preferably more than 90 mol%, even more preferably 100 mol%, of the radical R ¹ or the radical R ² .

Preferably, R ¹ is selected from either (i) long chain straight chain alkyl radicals of 16 to 26 carbon atoms or (ii) short chain, straight chain or branched alkyl radicals of 6 to 12 carbon atoms.

Preferably, R ² is selected from either (i) long chain straight chain alkyl radicals of 16 to 26 carbon atoms or (ii) short chain branched chain alkyl radicals of 6 to 12 carbon atoms or cycloalkyl radicals of 6 to 12 carbon atoms.

Preferably, R ³ is selected from either (i) long chain straight chain alkyl radicals of 16 to 26 carbon atoms or (ii) short chain branched chain alkyl radicals of 6 to 12 carbon atoms or cycloalkyl radicals of 6 to 12 carbon atoms. Preferably, the short-chain component (ii) is unbranched or branched (preferably branched) alkyl radicals having 8 to 12 carbon atoms or cycloalkyl radicals having 6 to 12 carbon atoms. Preferably, the long chain component (i) is straight chain alkyl radicals of 18 to 24 carbon atoms, more preferably 20 to 22 carbon atoms.

Preferably, R ^{1 is} an unbranched alkyl radical of 20 to 22 carbon atoms, R ^{2 is} a branched alkyl radical of 8 carbon atoms (especially 2-ethylhexyl acrylate), and R ³ is an unbranched alkyl radical of 20 carbon atoms.

R ¹ is preferably an unbranched alkyl radical having 10 carbon atoms, R ^{2 is} an unbranched alkyl radical having 22 carbon atoms and R ³ is an un-branched alkyl radical having 20 carbon atoms.

Preferably, R ^{1 is} an unbranched alkyl radical of 20 to 22 carbon atoms, R ^{2 is} a cyclic alkyl radical of 6 carbon atoms, and R ³ is an unbranched alkyl radical of 20 carbon atoms.

Preferably, R ^{1 is} an unbranched alkyl radical of 20 to 22 carbon atoms, R ^{2 is} a branched alkyl radical of 8 carbon atoms, and R ³ is an unbranched alkyl radical of 20 carbon atoms. Preferably, R ^{1 is} an unbranched alkyl radical of 20 to 22 carbon atoms, R ^{2 is} an unbranched alkyl radical of 22 carbon atoms, and R ³ is a cyclic alkyl radical of 6 carbon atoms.

R ¹ is preferably an unbranched alkyl radical having 20 to 22 carbon atoms, R ² is an unbranched alkyl radical having 22 carbon atoms and R ³ is an unbranched alkyl radical having 12 carbon atoms.

Preferably, the copolymer of the invention has a weight average molecular weight in the range of 1000 to 50,000 g / mol.

Another object of the present invention is a process for preparing a copolymer according to the invention comprising the steps

(b) reacting the copolymer intermediate obtained in (a) with an alcohol R ³ -OH at least to partially ring-open maleic anhydride monomer present in the intermediate, wherein the variables R ¹ , R ² , R ³ , R ^a are as defined above and have preferred meanings.

Accordingly, a further object of the present invention is a copolymer obtainable by the process according to the invention. The copolymers according to the invention can be used as pour point improvers, paraffin inhibitors or viscosity reducers. Of course, use in one of these areas does not exclude simultaneous use in one or more other areas.

Accordingly, a further subject of the present invention is the use of a copolymer according to the invention as a pour point improver, paraffin inhibitor or viscosity reducer, especially in crude oils, at least partially refined oils, fuels or biofuels.

Another object of the present invention is a method for improving the pour point of a liquid for reducing the viscosity of a liquid with the step of contacting the copolymer of the invention with the liquid, wherein the liquid is in particular crude oil, at least partially refined oil, fuel or biofuel.

Examples

Experimental part:

A. Analytics GPC Analytics

Unless stated otherwise, the weight average molecular weight M _w and number average molecular weight M _{n of} the copolymers were measured by gel permeation chromatography (GPC). GPC separation was carried out using two PLge Mixed B columns (Agilent) in tetrahydrofuran at 35 ° C. The calibration was carried out by means of a narrowly distributed polystyrene standard (PSS, Germany) with molecular weight 162-50400 Da. Hexylbenzene was used as a low molecular weight marker.

B. Preparation Examples Example 1

Original: 153.62 g of C20-C24 olefin and 65.84 g of Solvesso® 150

Feed 1: 50.84 g of maleic anhydride (heated at 80 ° C.)

Feed 2: 95.54 g of 2-ethylhexyl acrylate

Feed 3: 3.46 g of di- tert. Butyl peroxide dissolved in 13.84 g of Solvesso® 150

In a 1 liter Pilotwerkrührer the template is heated to 150 ° C.

Feed 1, 2 and 3 are added within 3 hours and then polymerized for 1 hour.

In a reactor (1 liter pilot plant stirrer), 153.62 g of C20-C24 olefin and 65.84 g of Solvesso® 150 were initially charged. The mixture was stirred under nitrogen and with stirring Heated to 150 ° C. To this was added within 3 hours 3.46 g of di- tert. Butyl peroxide dissolved in 13.84 g of Solvesso® 150, molten maleic anhydride (50.84 g of maleic anhydride, heated at 80 ° C) and 95.54 g of 2-ethylhexyl acrylate. The reaction was stirred at 150 ° C for an additional hour and then cooled.

The product has a solids content of 78.4% (measured after 2 hours under vacuum at 120 ° C)

Appearance: yellow, clear, viscous

Implementation with alcohol

30 g of the product thus prepared were mixed together with 14.70 g Nafol 20 + BA and 9.90 g Solvesso 150 and stirred at 150 ° C AT over 4 hours. Subsequently, the product was waxy and yellow.

The solids content of the product is 66.7% (measured after 2 hours under vacuum at 120 ° C.) Example 2

Original: 96.83 g C12 olefin and 96.83 g Solvesso® 150

Feed 1: 63.43 g of maleic anhydride (heated at 80 ° C.)

Feed 2: 227.89 g of behenyl acrylate dissolved in 25.32 g of Solvesso® 150

Feed 3: 2.09 g of di- tert. Butyl peroxide dissolved in 1 1, 84 g of Solvesso® 150

In a 1 liter Pilotwerkrührer the template is heated to 150 ° C.

Feed 1, 2 and 3 are added within 3 hours and then polymerized for 1 hour.

96.83 g of C12 olefin and 96.83 g of Solvesso® 150 were initially introduced into a reactor (1 liter pilot plant stirrer). The mixture was heated to 150 ° C under a stream of nitrogen and with stirring. To this was added within 3 hours 2.09 g of di-tert. Butyl peroxide dissolved in 1 1, 84 g of Solvesso® 150, molten maleic anhydride (63.43 g of maleic anhydride, heated at 80 ° C) and 227.89 g of behenyl acrylate dissolved in 25.32 g Solvesso® 150. The reaction mixture was at 150 ° C stirred for an additional hour and then cooled.

The product has a solids content of 73.6% (measured under vacuum at 140 ° C until constant mass is reached).

Appearance: yellow, pasty

Implementation with alcohol

33 g of the product thus prepared were mixed together with 14.60 g of Nafol 20 + BA and stirred at 150 ° C AT over 4 hours. Subsequently, the product was yellow, milky cloudy, solid.

The solids content of the product is 82.2% (measured after 2 hours under vacuum at 120 ° C)

Example 3

Original: 158 g of C20-C24 olefin

Feed 1: 52.20 g of maleic anhydride (heated at 80 ° C.)

Feed 2: 89.71 g of cyclohexyl methacrylate Feed 3: 3.46 g of di- tert. Butyl peroxide dissolved in 13.84 g of Solvesso® 150

In a 1 liter Pilotwerkrührer the template is heated to 150 ° C.

Feed 1, 2 and 3 are added within 3 hours and then polymerized for 1 hour.

In a reactor (1 liter Pilotwerkrührer) 158 g of C20-C24 olefin were submitted. The mixture was heated to 150 ° C under a stream of nitrogen and with stirring. To this was added within 3 hours 3.46 g of di- tert. Butyl peroxide dissolved in 13.84 g of Solvesso® 150, molten maleic anhydride (52.20 g of maleic anhydride, heated at 80 ° C) and 89.71 g of cyclohexyl methacrylate. The reaction was stirred at 150 ° C for an additional hour and then cooled.

The product has a solids content of 100% (measured under vacuum for 2 h at 120 ° C) Appearance: white, solid.

Implementation with alcohol

25 g of the product thus prepared were mixed together with 16.09 g Nafol 20 + BA and 17 g Solvesso 150 and stirred at 150 ° C AT over 4 hours. Subsequently, the product was yellow, milky cloudy, solid.

The solids content of the product is 65.25% (measured after 2 hours under vacuum at 120 ° C).

Example 4

Template: 153.62 g of C20-C24 olefin

Feed 1: 50.84 g of maleic anhydride (heated at 80 ° C.)

Feed 2: 95.54 g of 2-ethylhexyl acrylate

In a 1 liter Pilotwerkrührer the template is heated to 150 ° C.

Feed 1, 2 and 3 are added within 3 hours and then polymerized for 1 hour.

In a reactor (1 liter Pilotwerkrührer) 153.6 g of C20-C24 olefin were submitted. The mixture was heated to 150 ° C under nitrogen flow with stirring. To this was added within 3 hours 3.46 g of di- tert. Butyl peroxide dissolved in 13.84 g of Solvesso® 150, molten maleic anhydride (50.84 g of maleic anhydride heated at 80 ° C) and 95.54 g of ethylhexyl acrylate. The reaction was stirred at 150 ° C for an additional hour and then cooled.

Implementation with alcohol

31.25 g of the product thus prepared were mixed together with 21.33 g of Nafol 20 + BA and 22.43 g of Solvesso 150 and stirred at 150 ° C. AT for 4 hours. Subsequently, the product was yellow, creamy-like.

The solids content of the product is 69.5% (measured after 2 hours under vacuum at 120 ° C). Example 5

Original: 79.37 g of C20-C24 olefin in 93.17 g of Solvesso® 150

Feed 1: 26.3 g of maleic anhydride (heated at 80 ° C.)

Feed 2: 94.37 g of behenyl acrylate

Feed 3: 2.31 g of di- tert. Butyl peroxide dissolved in 13.07 g of Solvesso® 150

In a 1 liter Pilotwerkrührer the template is heated to 150 ° C.

Feed 1, 2 and 3 are added within 3 hours and then polymerized for 1 hour.

In a reactor (1 liter Pilotwerkrührer) 79.37 g of C20-C24 olefin were submitted. The mixture was heated to 150 ° C under nitrogen flow with stirring. To this was added within 3 hours 2.31 g of di-tert. Butyl peroxide dissolved in 13.07 g of Solvesso® 150, molten maleic anhydride (26.3 g of maleic anhydride heated at 80 ° C) and 94.37 g of behenyl acrylate (melted at 60 ° C). The reaction was stirred at 150 ° C for an additional hour and then cooled.

The product has a solids content of 68.30% (measured under vacuum for 2 hours at 120 ° C.)

Appearance: yellow, clear, thin viscous

Implementation with alcohol

43.9 g of the product thus prepared were mixed together with 4.02 g of cyclohexanol and stirred at 150 ° C. AT for 4 hours. Subsequently, the product was yellow, milky cloudy, pasty

The solids content of the product is 70% (measured after 2 hours under vacuum at 120 ° C.) Example 6

Original: 79.37 g of C20-C24 olefin in 93.17 g of Solvesso® 150

Feed 1: 26.3 g of maleic anhydride (heated at 80 ° C.)

Feed 2: 94.37 g of behenyl acrylate

In a 1 liter Pilotwerkrührer the template is heated to 150 ° C.

Feed 1, 2 and 3 are added within 3 hours and then polymerized for 1 hour.

79.37 g of C20-C24 olefin and 93.17 g of Solvesso® 150 were initially charged in a reactor (1 liter pilot plant stirrer). The mixture was heated to 150 ° C under a stream of nitrogen and with stirring. To this was added within 3 hours 2.31 g of di-tert. Butyl peroxide dissolved in 13.07 g of Solvesso® 150, molten maleic anhydride (26.3 g of maleic anhydride heated at 80 ° C) and 94.37 g of behenyl acrylate (melted at 60 ° C). The reaction was stirred at 150 ° C for an additional hour and then cooled.

Appearance: yellow, clear, thin viscous

Implementation with alcohol 43.9 g of the product thus prepared were mixed together with 7.5 g of dodecanol and stirred at 160 ° C. AT for 4 hours. Subsequently, the product was yellow, milky cloudy, pasty The solids content of the product is 72.2% (measured after 2 hours under vacuum at 120 ° C)

Comparative Examples 1C-3C Example 1 C

Original: 800 g of C20-C24 olefin

Feed 1: 264.76 g of maleic anhydride (heated at 80 ° C.)

Feed 2: 10.86 g of di- tert. butyl

In a 1 liter Pilotwerkrührer the template is heated to 150 ° C.

Feed 1 and 2 are added within 5 hours and then postpolymerized for 1 hour.

In a reactor (1 liter Pilotwerkrührer) 800 g of C20-C24 olefin were submitted. The mixture was heated to 150 ° C under a stream of nitrogen and with stirring. To this was added within 5 hours 10.86 g of di-tert. Butyl peroxide, molten maleic anhydride (800 g maleic anhydride, heated at 80 ° C). The reaction was stirred at 150 ° C for an additional hour and then cooled.

The product has a solids content of 100% (measured under vacuum for 2 h at 120 ° C)

Appearance: yellowish solid product

Implementation with alcohol

280 g of the product thus prepared were stirred together with 265 g of Nafol 20 + BA and mixed and 136.3 g of Solvesso 150 at 160 ° C. AT for 4 hours. Then the product was beige, solid.

The solids content of the product is 80% (measured after 2 hours under vacuum at 120 ° C)

Example 2 C

Template: 153.62 g of C20-C24 olefin

Feed 1: 50.84 g of maleic anhydride (heated at 80 ° C.)

Feed 2: 95.54 g of 2-ethylhexyl acrylate

In a 1 liter Pilotwerkrührer the template is heated to 150 ° C.

Feed 1, 2 and 3 are added within 3 hours and then polymerized for 1 hour. In a reactor (1 liter Pilotwerkrührer) 153.6 g of C20-C24 olefin were submitted. The mixture was heated to 150 ° C under a stream of nitrogen and with stirring. To this was added within 3 hours 3.46 g of di- tert. Butyl peroxide dissolved in 13.84 g of Solvesso® 150, molten maleic anhydride (50.84 g of maleic anhydride, heated at 80 ° C) and 95.54 g of 2-ethylhexyl acrylate. The reaction was stirred at 150 ° C for an additional hour and then cooled.

Implementation with alcohol

40.00 g of the product thus prepared were mixed together with 12.51 g of Nafol 20 + BA and 6.44 g of dodecanol and stirred at 160 ° C. AT for 4 hours. Subsequently, the product was bright yellow, waxy

The solids content of the product is 97.6% (measured after 2 hours under vacuum at 120 ° C)

Example 3 C

Original: 60 g Solvesso® 150

Feed 1: 55.04 g of maleic anhydride (heated at 80 ° C.)

Feed 2: 197.73 g of behenyl acrylate

Feed 3: 4.47 g of di- tert. Butyl peroxide dissolved in 25.33 g of Solvesso® 150

Feed 4: 47.23 g hexenes in 55.45 g Solvesso® 150

In a 1 liter Pilotwerkrührer the template is heated to 150 ° C.

Feed 1, 2, 3 and 4 are added within 3 hours and then polymerized for 1 hour.

In a reactor (1 liter pilot plant stirrer) 60 g Solvesso® 150 were submitted. The mixture was heated to 150 ° C under a stream of nitrogen and with stirring. To this was added within 4 hours 4.47 g of di-tert. Butyl peroxide dissolved in 25.33 g of Solvesso® 150, molten maleic anhydride (55.04 g of maleic anhydride heated at 80 ° C) and 197.73 g of behenyl acrylate (melted at 60 ° C) and 47.23 g of hexene dissolved in 55 , 45 g Solvesso® 150. The reaction mixture was stirred at 150 ° C for an additional hour and then cooled.

The product has a solids content of 67.6% (measured under vacuum for 2 h at 120 ° C)

Appearance: bright yellow, cloudy, pasty.

Implementation with alcohol

37.00 g of the product thus prepared were mixed together with 16.90 g Nafol 20 + BA and stirred at 160 ° C AT over 4 hours. Subsequently, the product was bright yellow, cloudy, waxy, solid

The solids content of the product is 80.1% (measured after 2 hours under vacuum at 120 ° C) For MSA Olefin Acrylate Alcohol 1 Alcohol 2 Mn Mw play R ¹ R ² (i) R ³ (ii) R ³

1 C C20 (i) 0 C20 0 6000 12000

0.5 mol 0.5 mol 0.5 mol

2C C20 (i) C8 cont. (ii) C 20 C 12 4850 21900

0.33 mol 0.33 mol 0.33 mol 0.17 mol 0.17 mol

3C C4 (ii) C22 (i) C20 O 2420 5020

0.33 mol 0.33 mol 0.33 mol 0.33 mol

1 C20 (i) C8 cont. (ii) C20 0 2360 5950

0.33 mol 0.33 mol 0.33 mol 0.33 mol

2 C10 (ii) C22 (i) C20 O 3050 7000

0.33 mol 0.33 mol 0.33 mol 0.33 mol

3 C20 (i) C6 cycl. (ii) C20 O 3530 16700

0.33 mol 0.33 mol 0.33 mol 0.33 mol

4 C20 (i) C8 cont. (ii) C20 O 4850 21900

0.33 mol 0.33 mol 0.33 mol 0.33 mol

5 C20 (i) C22 (i) 0 C6 cycl. 2180 4600

0.33 mol 0.33 mol 0.33 mol 0.33 mol

6 C20 (i) C22 (i) 0 C12 2180 4600

0.33 mol 0.33 mol 0.33 mol 0.33 mol

The solids content of the product is 72% (measured after 2 hours under vacuum at

120 ° C)

Testing of the additives as pour point depressants (*):

To measure the point point, a pour point tester 45150 from PSL from Osterode am Harz, Germany is used. The measurement is analogous to ASTM D5985. For testing a Rohrerdöl from Landau, Germany by the company. Wintershall is used. The oil has an API of 37.

A 21 crude oil bottle is 30min. tempered at 80 ° C in a water bath. The bottle is shaken vigorously during the tempering for homogenization (Caution: low-boiling hydrocarbons may outgas). 50 ml crude oil are added in 100 ml plastic bottles and tempered for a further 15 minutes at 80 ° C in a water bath. A 10% solution of the additive in Solvesso 150 is then metered in according to the concentrations while shaking the mixture oil / additive vigorously. The sample (oil and additive) is heated for a further 15 minutes at 80 ° C and then shaken vigorously again. Afterwards, about 30 ml of the sample are placed in the containers provided up to the ring mark on the inside of the cup and closed with a cork stopper. The sample is tempered again at 80 ° C for 10 minutes. The container is then removed from the water bath, placed in the holder of the PP tester and turned until it clicks into place. The sensor head is dipped counterclockwise over the sample cup. The telescopic cylinder is gently moved back and forth until it engages over the guide ring of the holder. The measurement is then started. One recognizes a reduction in the pour point by the addition of the additive (see table). The PP of crude oil without additives is. 21 ° C

Measuring pour points of the 20% solution of the product in Solvesso 150 (**)

To measure the point point, a pour point tester 45150 from PSL from Osterode am Harz, Germany is used. The measurement is analogous to ASTM D5985. To measure the pour point, a 20% solution of the product is taken in Solvesso 150.

This solution is filled (about 30 ml of the sample) in the containers provided up to the ring mark on the inside of the cup. The sample is placed in the holder of the PP tester and rotated until it snaps into place. The sensor head is dipped counterclockwise over the sample cup. The telescopic cylinder is gently moved back and forth until it engages over the guide ring of the holder. The measurement is then started.

It shows good PPD values in all examples of the invention an improved PP value.

Claims

claims

Copolymer containing the monomer units

H R 'H R H H

I I I I I

-hc-c + -hc-c + -f -c -c-

(A) HH _(B) HC (O) OR ² _{and (C)} HO (O) CC (O) OR ³ where

R ^{a is} hydrogen or methyl,

R ¹ , R ² , R ^{3 are} either (i) long-chain, unbranched alkyl radicals having 16 to 26 carbon atoms or (ii) short-chained, unbranched or branched alkyl radicals having 6 to 12 carbon atoms or cycloalkyl radicals having 6 to 12 carbon atoms,

the sum of the monomer units (A), (B) and (C) is more than 50 mol% based on the total sum of all monomer units in the copolymer and from 20 mol% to 40 mol% of the monomer units (A), (B) , (C) based on the sum of the monomer units (A), (B), (C) radicals R ¹ , R ² , R ³ , which are selected from the radicals (ii).

Copolymer according to claim 1, characterized in that the long-chain radicals (i) have 18 to 24 carbon atoms.

Copolymer according to claim 1 or 2, characterized in that cycloalkyl radicals are present.

Copolymer according to claim 1 or 2, characterized in that no cycloalkyl radicals are present.

5. Copolymer according to one or more of claims 1 to 4, characterized in that the radicals (ii) have 6 to 10 carbon atoms.

Copolymer according to one or more of claims 1 to 5, characterized in that 30 mol% to 35 mol% of the monomer units (A), (B), (C) based on the sum of the monomer units (A), (B) , (C) radicals R ¹ , R ² , R ³ , which are selected from the radicals (ii). 7. Copolymer according to one or more of claims 1 to 6, characterized in that based on the sum of all radicals R ¹ , R ² , R ³ , which are selected from radicals (ii), more than 50 mol% of the radical R ^{2 are} assigned. 17

8. Copolymer according to one or more of claims 1 to 6, characterized in that based on the sum of all radicals R ¹ , R ² , R ³ , which are selected from radicals (ii), more than 50 mol% of the radical R ^{1 are} assigned.

Copolymer according to one or more of claims 1 to 8, characterized in that the sum of the monomer units (A), (B) and (C) based on the total sum of all monomer units in the copolymer is at least 60 mol%.

Copolymer according to one or more of claims 1 to 9, characterized in that the weight average molecular weight of the copolymer is in the range of 1000 to 50,000 g / mol.

1 1. Process for the preparation of a copolymer according to one or more of Claims 1 to 10 comprising the steps of free-radical polymerization of maleic anhydride (C) with a monomer of formula (Α ') R ¹ -CH = CH ₂ and a monomer of formula (Β') CH ₂ = C (R ^a ) C (O) OR ² and

Reaction of the copolymer intermediate obtained in (a) with an alcohol R ³ -OH at least partially ring opening of maleic anhydride monomers present in the intermediate.

Use of a copolymer according to any one of claims 1 to 10 as a pour point improver, paraffin inhibitor or viscosity reducer.

Use according to claim 12 in crude oils, at least partially refined oils, fuels or biofuels.