EP0236844B1 - Use of additives for mineral oils with modified pour- point characteristics - Google Patents

Description

Field of the Invention

The invention relates to the use of additives for mineral oils, in particular for distillate oils with a pour point-improving effect based on alkyl methacrylates.

State of the art

Mineral oils, e.g. Commercial distillate oils generally contain n-paraffin hydrocarbons, which on the one hand have a favorable effect on the setting of a good viscosity / temperature behavior, but on the other hand fail in crystalline form on cooling and thereby impair the flow of the oils or completely prevent them ("stagnation") . An improvement in the low-temperature flow properties can be achieved by dewaxing. Since the costs increase considerably if one wants to lower the "pour point" beyond certain values, one generally only partially dewaxes the oils to a pour point in the range of minus 15 degrees Celsius and uses the further reduction Pour point (up to about minus 40 degrees Celsius) so-called pour point depressants, which effectively reduce the pour point in concentrations between 0.05 and 1%. The following idea is decisive:

Paraffin-like compounds are built into the growing paraffin crystal surfaces and thus prevent the crystals from growing further and the formation of extensive crystal groups.

For the mode of operation of such pour point improvers, it applies that they have certain structural elements, namely sufficiently long alkyl groups to be incorporated into the growing paraffin crystals from the nucleation and side chains or side groups at greater intervals to disrupt the crystal growth. (See Ullmanns, Encyklopedia of technical chemistry, 4th edition, volume 20, Verlag Chemie, 1981, p. 548). Technically applicable pour point depressants, on the other hand, must be required to have good thermal, oxidative and chemical stability, shear strength and the like. have.

zwischen ca. 5 000 und 500 000, die eine Verbesserung des Fließverhaltens von leichten, niedermolekularen bis zu schweren, hochmolekularen Schmierölen gestatten.
Bekanntlich haben sich auch Olefincopolymerisate (OCP's) unter verschiedenen Anwendungs-Gesichtspunkten als Mineralöladditive in der Praxis bewährt. (Vgl. DE-AS 1 235 491).The currently preferred pour point depressants are polymethacrylates, which lower the pour point of lubricating oils sufficiently in concentrations of 0.1-0.5% (cf. US Pat. No. 2,091,627, US Pat. No. 2,100,993, US Pat. PS 2 114 233). The carbon number of the alkyl radicals is between 12 and 18, the degree of branching between 10 and 30 mol%. Polymethacrylates are available in the area $\overline{\text{M}}$

between approx. 5,000 and 500,000, which allow an improvement in the flow behavior of light, low-molecular to heavy, high-molecular lubricating oils.
As is known, olefin copolymers (OCP's) have also proven themselves in practice as mineral oil additives from various application points of view. (See DE-AS 1 235 491).

720 - 1400) durch Hochdruckpolymerisation in Anwesenheit von Reglern, die als Stockpunktsverbesserer wirken.Relatively much attention was therefore paid to copolymers from these two polymer classes. DE-OS 21 02 469 describes, inter alia, low molecular weight copolymers of ethylene with methyl methacrylate or 2-ethylhexyl acrylate (M. $\overline{\text{W}}$

720 - 1400) High pressure polymerization in the presence of regulators, which act as pour point improvers.

In the European Patent application 113,591 are described as lubricating oil and fuel additives, hydrogenated emulsion copolymers of 1,3-butadiene and alkyl (meth) acrylate, which can be used as VI improvers and pour point improvers. These polymers have a dispersing effect if they are grafted with polar, nitrogen-containing monomers.
DE-OS 26 12 232 recommends a combination of an ethylene-isobutyl acrylate copolymer and a polytetradecyl acrylate or hexadecyl methacrylate-methyl methacrylate copolymer as an additive for petroleum distillates (bp 120-480 degrees Celsius) to regulate wax crystal formation in the low temperature range.
The reaction products of a long-chain alkyl acrylate or methacrylate, a C1-C4-alkyl acrylate or methacrylate and acrylic acid, which has been neutralized with 1-hydroxy-2-alkyl- or alkylidene imidazoline, are described as viscosity index improvers with dispersing action in the US PS 3 397 146 recommended.

The teaching of FR-A 1 235 693 also relates to polymeric VI improvers based on poly (meth) acrylic esters with vinylpyridine as a co-monomer, the practical application concentrations being ≥ 1.5% being in line with VI's usual practice -Improve.

• I. aus 10 - 99 Gew.-% an Polymeren P1, die
  • a) aus (Meth)acrylsäureestern von geradkettigen, unverzweigten C6-C15-Alkoholen mit 6 bis 15 Kohlenstoffatomen und
  • b) aus (Meth)acrylsäureestern von geradkettigen unverzweigten C16-C30-Alkoholen und
  • c) aus (Meth)acrylsäureestern mit verzweigten C8-C40-Alkoholen,
  • d) aus (Meth)acrylsäureestern von C1-C5-Kohlenstoffatomen,
  • e) aus Monomeren, mit funktionellen Gruppen aufgebaut sind,
  wobei der Anteil an b) höchstens 5 Mol-% ausmacht, und
• II. aus 90 - 1 Gew.-% an Polymeren P2, die
  • a') aus (Meth)acrylsäureestern von geradkettigen unverzweigten C6-C15-Alkoholen und
  • b') aus (Meth)acrylsäureestern von geradkettigen, unverzweigten C16-C30-Alkoholen und
  • c') aus (Meth)acrylsäureestern von verzweigten C8-C40-Alkoholen und
  • d') aus (Meth)acrylsäureestern von C1-C5-Alkoholen aufgebaut sind,
  • e') aus Monomeren mit funktionellen Gruppen
  enthalten, wobei der Anteil an b') 10 - 70 Mol-% ausmacht, mit einem Lösungsmittel (L).

In DE-OS 21 45 249, polymethacrylates produced using amines as initiators are recommended as lubricating oil additives. The production of polybutyl methacrylate with a molecular weight of 455,000 was carried out as an example.
Furthermore, additives have been developed for lubricating oils containing n-paraffin, which are based on mixtures of different acrylate polymers (DE-OS 33 39 103). These mixtures exist

• I. from 10 - 99 wt .-% of polymers P1, the
  • a) from (meth) acrylic acid esters of straight-chain, unbranched C6-C15 alcohols with 6 to 15 carbon atoms and
  • b) from (meth) acrylic acid esters of straight-chain unbranched C16-C30 alcohols and
  • c) from (meth) acrylic acid esters with branched C8-C40 alcohols,
  • d) from (meth) acrylic acid esters of C1-C5 carbon atoms,
  • e) are composed of monomers with functional groups,
  the proportion of b) being at most 5 mol%, and
• II. From 90-1% by weight of polymers P2, the
  • a ') from (meth) acrylic acid esters of straight-chain unbranched C6-C15 alcohols and
  • b ') from (meth) acrylic acid esters of straight-chain, unbranched C16-C30 alcohols and
  • c ') from (meth) acrylic acid esters of branched C8-C40 alcohols and
  • d ') are composed of (meth) acrylic acid esters of C1-C5 alcohols,
  • e ') from monomers with functional groups
  included, the proportion of b ') being 10-70 mol%, with a solvent (L).

DE-A-1 444 884 claims copolymers dissolved in oil based on acrylic esters, the polymer being a graft copolymer made from at least one alkyl acrylate or methacrylate, the alkyl radical of which ensures oil solubility. Units of maleamic or itaconamic acids, which make up 1-22% by weight of the graft copolymer, are grafted onto this polymer. To the extent that these graft copolymers have been used to lower the "pour point", they are used in additional amounts of 1% by weight.

It appears remarkable that pour point improvers containing methyl methacrylate have so far not been used in practice. The justified one should be Expectations have played a role that products that contain methyl methacrylate in substantial proportions only develop a satisfactory effect with higher additions.

Task and solution

It was still the task to provide pour point improving additives for mineral oils, in particular distillate oils on a paraffinic basis, which with undiminished efficiency, i.e. acting in approximately the same application concentrations, should be able to be produced as inexpensively as possible. In particular, the replacement of the relatively expensive higher alkyl esters was to be considered.

• a) 10 - 30 Molprozent, vorzugsweise 10 - 20 Molprozent Methylmethacrylat
• b) 10 - 70 Molprozent, vorzugsweise 10 - 50 Molprozent Alkylmethacrylaten mit unverzweigten Alkylestern mit 16 - 30 Kohlenstoffatomen im Alkylrest und
• c) 80 - 0 Molprozent, vorzugsweise 80 - 30 Molprozent, insbesondere 80 - 50 Molprozent Alkylmethacrylaten mit unverzweigten Alkylresten mit 4 - 15, vorzugsweise 6 - 15 Kohlenstoffatomen und/oder verzweigten Alkylresten mit 4 - 40, vorzugsweise 8 - 30, Kohlenstoffatomen im Alkylrest und als Monomerkomponente

mit der Massgabe,
daß die Monomerkomponente b) aus mehreren unter sich verschiedenden Alkylmethacrylaten besteht, als Öladditive, wobei die Polyalkylmethacrylate P in Mengen zwischen 0.05 und 1 Gew.-% als Stockpunkt-Verbesserer in Mineralölen eingesetzt werden.It has now been found that the above-mentioned object can be achieved in a particularly favorable manner by means of the use of defined additives according to the invention as pour point improvers in mineral oils. The additives to be used according to the invention with a pour point-improving effect consist of a polymethacrylate P in the form of statis

• a) 10-30 mole percent, preferably 10-20 mole percent methyl methacrylate
• b) 10-70 mol percent, preferably 10-50 mol percent of alkyl methacrylates with unbranched alkyl esters with 16-30 carbon atoms in the alkyl radical and
• c) 80-0 mol percent, preferably 80-30 mol percent, in particular 80-50 mol percent, of alkyl methacrylates with unbranched alkyl radicals having 4-15, preferably 6-15 carbon atoms and / or branched alkyl radicals with 4-40, preferably 8-30, carbon atoms in the alkyl radical and as a monomer component

with the proviso
that the monomer component b) consists of several different alkyl methacrylates, as oil additives, the polyalkyl methacrylates P being used in amounts between 0.05 and 1% by weight as pour point improvers in mineral oils.

The nature of the polymers P as statistical copolymers results, inter alia, from the general preparation instructions given below.

w/ $\overline{\text{M}}$

n) der Polymeren P im Bereich 1,5 bis 5,0.
Der Staudinger-Index beträgt 10 - 150 ml/g in Chloroform bei 20 Grad Celsius.The polymers P preferably have a molecular weight range of 10,000 to 800,000. The molecular weight can be determined in a manner known per se by means of gel permeation chromatography. (See Vieweg-Braun, Kunststoff-Handbuch, Volume I, Carl Hanser Verlag, 1975). The inconsistencies are usually ( $\overline{\text{M}}$

w / $\overline{\text{M}}$

n) the polymer P in the range 1.5 to 5.0.
The Staudinger index is 10 - 150 ml / g in chloroform at 20 degrees Celsius.

A preferred embodiment of the invention provides that, provided that the proportion of unbranched alkyl methacrylates having 4 to 15 carbon atoms in the alkyl radical is in the range 35-45 mol% based on the polymer P, the proportion of component b) in the polymer P 20 to 30 mol% should be.
A further preferred embodiment of the invention is that the proportion of unbranched alkyl methacrylates having 4 to 15 carbon atoms in the alkyl radical is in the range 15-30 mol%, and the proportion of component b) in the polymer P is 25 to 40 mol%. % should be. Furthermore, a likewise preferred embodiment of the invention provides that if the proportion of unbranched alkyl methacrylates having 4 to 15 carbon atoms in the alkyl radical is zero mol%, the proportion of component b) in the polymer P is 30 to 50 mol%.

The monomers for components a) - c) of the polymers P are known per se.
Suitable monomers for component b) are the methacrylic acid esters of straight-chain, unbranched C16-C30 alkanols, in particular unbranched C16-C24 alkanols, especially C18-C22 alcohols. Commercial products such as tallow fatty alcohols and those sold under the name Alfole R (product from Condea, Hamburg) are particularly worth mentioning. Different esters can thus also form the monomers of type b). Such mixtures can be considered advantageous.
The monomers of component c) are, on the one hand, the methacrylic acid esters of the straight-chain, unbranched C4-C15 alkanols. Examples include the straight-chain, unbranched C10-C14 alcohols, particularly those obtained by the Ziegler process by hydrolysis of aluminum alkoxides.
Examples include the Lorole R from Henkel KG, Düsseldorf and the Alfole R from Condea, Hamburg.
On the other hand, the monomers of component c) are the methacrylic acid esters of branched alkanols having 4 to 40 carbon atoms in the molecule, in particular the branched C8-C20 alcohols of the isoalkanol type, especially isodecyl, isotridecyl and isooctodecyl alcohol.

der Polymerisate P liegen besonders bevorzugt im Bereich 50 000 bis 500 000.The molecular weights $\overline{\text{M}}$

the polymers P are particularly preferably in the range from 50,000 to 500,000.

The polymers P can be prepared by the customary free-radical polymerization processes. (See H. Rauch-Puntigam, Th. Völker: Acryl- und Methacrylverbindungen, Springer-Verlag, Berlin, 1967).

Preparation of the polymers P

The preparation of the polymers follows the polymerization processes of the prior art. A mixture of mineral oil and a monomer mixture of a), b) and c) is placed in a reaction vessel which is expediently equipped with a stirrer, thermometer, reflux condenser and metering line, insofar as the latter are used. The mixture is heated to approx. 90 - 100 degrees Celsius under a C02 atmosphere and stirring. After this temperature has been reached and initiator (preferably per compounds such as peresters, peroxides or azo compounds) has been added, a mixture of the monomers a), b) and c) and further initiator is metered in; approx. 2 hours after the end of the feed, another initiator becomes replenished. The total amount of initiator is usually 1-3% by weight, based on the total amount of monomers. The total polymerization time is generally 8-9 hours. A viscous solution with a polymer content of generally 40-70% by weight is obtained.

Oil mixture for measuring the pour point, the low-temperature viscosity and the "stable pour point"

The additive, possibly together with other additives such as DI package and OCP-VI improvers, is dissolved in the base oil at 50 - 60 degrees Celsius while stirring.

Use of additives

The additives according to the invention can be added to the mineral oils in a manner known per se. According to the invention, an addition of 0.1 to 1.0% by weight is provided for pour point improvers. The mineral oils available have already been discussed above (cf. prior art). General information can be found in Ullmann, Vol. 20, loc.cit., Pg. 457-503.

Advantageous effects of the invention lie in an improved effectiveness in certain mineral oils and a broader spectrum of activity in mineral oils of different viscosity.

Oil formulations containing the additives according to the invention, in addition to the required viscosity data at 100 degrees Celsius, show very favorable values for pour point and stable pour point as well as excellent viscosity data at minus 15 degrees Celsius to minus 40 degrees Celsius.

Characterization can be carried out using the following measured variables: Pourpoint / Cloudpoint: DIN 51 497 Pour stability (stable pour point): Fed. Test. Meth. 203 No. 791 / Cycle C MRV viscosity: ASTM D 3829 CCS viscosity: DIN 51 377 Brookfield viscosity: DIN 51 398

Examples Manufacture of additives: Additive A

300 g

Mineralöl (η_{100 Grad Celsius} = 3,9 qmm/s)

21,00 g

Methacrylsäureester eines C12-C15-Alkoholgemisches mit 23 % verzweigten Alkoholen

8,97 g

Methacrylsäureester eines unverzweigten C16-C18 Alkoholgemisches

3,33 g

Methylmethacrylat

0,13 g

Dodecylmercaptan

0,36 g

tert.-Butylperoctoat

Nach Lösen der Komponenten wird bei 100 Grad Celsius nachstehendes Gemisch über einen Zeitraum von 210 Minuten zudosiert.

420,62 g

Methacrylsäureester eines C12-C15-Alkoholgemisches mit 23 % verzweigten Alkoholen

179,41 g

Methacrylsäureester eines unverzweigten C16-C18-Alkoholgemisches

66,67 g

Methylmethacrylat

2,67 g

Dodecylmercaptan

2,0 g

tert.-Butylperoctoat

Zwei Stunden nach Zulaufende wird mit 1,4 g tert.-Butylperoctoat nachgefüttert.
Gesamtpolymerisationszeit 8 Stunden. Es wird eine klare, viskose Lösung erhalten.The following mixture is placed in a 2 l four-necked flask with stirrer, thermometer, reflux condenser and metering line:

300 g

Mineral oil (η _{100 degrees Celsius} = 3.9 qmm / s)

21.00 g

Methacrylic acid ester of a C12-C15 alcohol mixture with 23% branched alcohols

8.97 g

Methacrylic acid ester of an unbranched C16-C18 alcohol mixture

3.33 g

Methyl methacrylate

0.13 g

Dodecyl mercaptan

0.36 g

tert-butyl peroctoate

After the components have been dissolved, the following mixture is metered in over a period of 210 minutes at 100 degrees Celsius.

420.62 g

Methacrylic acid ester of a C12-C15 alcohol mixture with 23% branched alcohols

179.41 g

Methacrylic acid ester of an unbranched C16-C18 alcohol mixture

66.67 g

Methyl methacrylate

2.67 g

Dodecyl mercaptan

2.0 g

tert-butyl peroctoate

Two hours after the end of the feed, 1.4 g of tert-butyl peroctoate are added.
Total polymerization time 8 hours. A clear, viscous solution is obtained.

Polymer content = 70% by weight.

• 24 Mol-% a)
• 20 Mol-% b)
• 56 Mol-% c)

   davon 43 Mol-% Bestandteil, der als unverzweigte C4-C15-Alkylmethacrylate zu klassieren ist.Viscosity (100 degrees Celsius, 70% by weight) = 800 qmm / s Composition:

• 24 mol% a)
• 20 mol% b)
• 56 mol% c)

43 mol% of which is to be classified as unbranched C4-C15 alkyl methacrylates.

Additive B Production as additive A, but

Vorlage:

300 g  Mineralöl (η_{100 Grad Celsius} = 3,9 qmm/s)
25,8 g  Methacrylsäureester eines C12-C15-Alkoholgemisches mit 23 % verzweigten Alkoholen
7,5 g  Methacrylsäureester eines unverzweigten C16-C18-Alkoholgemisches
0,13 g  Dodecylmercaptan
0,36 g  tert.-Butylperoctoat

Zulauf:

517,4 g  Methacrylsäure eines C12-C15-Alkoholgemisches mit 23 % verzweigten Alkoholen
149,3 g  Methacrylsäureester eines unverzweigten C16-C18-Alkoholgemisches
2,67 g  Dodecylmercaptan
2,0 g  tert.-Butylperoctoat

Polymerisatgehalt = 70 %
Viskosität (100 Grad Celsius, 70 Gew.-%ig) = 560 qmm/s Zusammensetzung:

• 0 Mol-% a)
• 20 Mol-% b)
• 79 Mol-% c)

   davon 62 Mol-%, die als unverzweigte C4-C15-Alkylmethacrylate zu klassieren sind.

Template:

300 g mineral oil (η _{100 degrees Celsius} = 3.9 qmm / s)
25.8 g of methacrylic acid ester of a C12-C15 alcohol mixture with 23% branched alcohols
7.5 g of methacrylic acid ester of an unbranched C16-C18 alcohol mixture
0.13 g dodecyl mercaptan
0.36 g of tert-butyl peroctoate

Intake:

517.4 g methacrylic acid of a C12-C15 alcohol mixture with 23% branched alcohols
149.3 g of methacrylic acid ester of an unbranched C16-C18 alcohol mixture
2.67 g dodecyl mercaptan
2.0 g of tert-butyl peroctoate

Polymer content = 70%
Viscosity (100 degrees Celsius, 70% by weight) = 560 qmm / s Composition:

• 0 mol% a)
• 20 mol% b)
• 79 mol% c)

62 mol% of which are classified as unbranched C4-C15-alkyl methacrylates.

Additive C

Vorlage:

360 g  Mineralöl (η_{100 Grad Celsius} = 3,9 qmm/s)
18,56 g  Methacrylsäureester eines unverzweigten C16-C18-Alkoholgemisches
4,0 g  Methacrylsäureester eines unverzweigten C12-C14-Alkoholgemisches
15,2 g  Methacrylsäureester eines C12-C15-Alkoholgemisches mit 60 % verzweigten Alkoholen
2,24 g  Methylmethacrylat
1,4 g  tert.-Butylperoctoat

Zulauf:

371,2 g  Methacrylsäureester eines unverzweigten C16-C18-Alkoholgemisches
80,0 g  Methacrylsäureester eines unverzweigten C12-C14-Alkoholgemisches
304,0 g  Methacrylsäureester eines C12-C15-Alkoholgemisches mit 60 % verzweigten Alkoholen
44,8 g  Methylmethacrylat
8,0 g  tert.-Butylperoctoat

Polymerisatgehalt = 70 %
Viskosität (100 Grad Celsius, 70 Gew.-%ig) = 680 qmm/s Zusammensetzung:

• 15 Mol-% a)
• 38 Mol-% b)
• 47 Mol-% c)

   davon 25 Mol-%, die als unverzweigte C4-C15-Alkylmethacrylate zu klassieren sind.Production as additive A, but

Template:

360 g mineral oil (η _{100 degrees Celsius} = 3.9 qmm / s)
18.56 g methacrylic acid ester of an unbranched C16-C18 alcohol mixture
4.0 g of methacrylic acid ester of an unbranched C12-C14 alcohol mixture
15.2 g of methacrylic acid ester of a C12-C15 alcohol mixture with 60% branched alcohols
2.24 g methyl methacrylate
1.4 g of tert-butyl peroctoate

Intake:

371.2 g methacrylic acid ester of an unbranched C16-C18 alcohol mixture
80.0 g methacrylic acid ester of an unbranched C12-C14 alcohol mixture
304.0 g methacrylic acid ester of a C12-C15 alcohol mixture with 60% branched alcohols
44.8 g methyl methacrylate
8.0 g of tert-butyl peroctoate

Polymer content = 70%
Viscosity (100 degrees Celsius, 70% by weight) = 680 qmm / s Composition:

• 15 mol% a)
• 38 mol% b)
• 47 mol% c)

25 mol% of which are classified as unbranched C4-C15 alkyl methacrylates.

Additive D

Vorlage:

360 g  Mineralöl (η_{100 Grad Celsius} = 3,9 qmm/s)
17,08 g  Methacrylsäureester eines unverzweigten C16-C18-Alkoholgemisches
22,92 g  Methacrylsäureester eines C12-C15-Alkoholgemisches mit 60 % verzweigten Alkoholen
1,4 g  tert.-Butylperoctoat

Zulauf:

341,6 g  Methacrylsäureester eines unverzweigten C16-C18-Alkoholgemisches
458,4 g  Methacrylsäureester eines C12-C15-Alkoholgemisches mit 60 % verzweigten Alkoholen
8,0 g  tert.-Butylperoctoat

Polymerisatgehalt: 70 %
Viskosität (100 Grad Celsius, 70 Gew.-%ig) = 560 qmm/s Zusammensetzung:

• 0 Mol-% a)
• 38 Mol-% b)
• 62 Mol-% c)

   davon 25 Mol-%, die als unverzweigte C4-C15-Alkylmethacrylate zu klassieren sind.

Production as additive A, but

Template:

360 g mineral oil (η _{100 degrees Celsius} = 3.9 qmm / s)
17.08 g methacrylic acid ester of an unbranched C16-C18 alcohol mixture
22.92 g of methacrylic acid ester of a C12-C15 alcohol mixture with 60% branched alcohols
1.4 g of tert-butyl peroctoate

Intake:

341.6 g of methacrylic acid ester of an unbranched C16-C18 alcohol mixture
458.4 g of methacrylic acid ester of a C12-C15 alcohol mixture with 60% branched alcohols
8.0 g of tert-butyl peroctoate

Polymer content: 70%
Viscosity (100 degrees Celsius, 70% by weight) = 560 qmm / s Composition:

• 0 mol% a)
• 38 mol% b)
• 62 mol% c)

25 mol% of which are classified as unbranched C4-C15 alkyl methacrylates.

Additive E

Vorlage:

300 g  Mineralöl (η_{100 Grad Celsius} = 3,9 qmm/s)
19,31 g  Methacrylsäureester eines C12-C15-Alkoholgemisches mit 23 % verzweigten Alkoholen
10,66 g  Methacrylsäureester eines unverzweigten C16-C18-Alkoholgemisches
3,33 g  Methylmethacrylat
0,13 g  Dodecylmercaptan
0,36 g  tert.-Butylperoctoat

Zulauf:

386,69 g  Methacrylsäureester eines C12-C15-Alkoholgemisches mit 23 % verzweigten Alkoholen
213,34 g  Methacrylsäureester eines unverzweigten C16-C18-Alkoholgemisches
66,67 g  Methylmethacrylat
2,67 g  Dodecylmercaptan
2,00 g  tert.-Butylperoctoat

Polymerisatgehalt: 70 %
Viskosität (100 Grad Celsius, 70 Gew.-%ig) = 800 qmm/s Zusammensetzung:

• 24 Mol-% a)
• 24 Mol-% b)
• 52 Mol-% c)

   davon 40 Mol-%, die als unverzweigte C4-C15-Alkylmethacrylate zu klassieren sind.Production as additive A, but

Template:

300 g mineral oil (η _{100 degrees Celsius} = 3.9 qmm / s)
19.31 g methacrylic acid ester of a C12-C15 alcohol mixture with 23% branched alcohols
10.66 g of methacrylic acid ester of an unbranched C16-C18 alcohol mixture
3.33 g methyl methacrylate
0.13 g dodecyl mercaptan
0.36 g of tert-butyl peroctoate

Intake:

386.69 g of methacrylic acid ester of a C12-C15 alcohol mixture with 23% branched alcohols
213.34 g of methacrylic acid ester of an unbranched C16-C18 alcohol mixture
66.67 g methyl methacrylate
2.67 g dodecyl mercaptan
2.00 g of tert-butyl peroctoate

Polymer content: 70%
Viscosity (100 degrees Celsius, 70% by weight) = 800 qmm / s Composition:

• 24 mol% a)
• 24 mol% b)
• 52 mol% c)

40 mol% of which are classified as unbranched C4-C15 alkyl methacrylates.

Additive F

Vorlage:

300 g  Mineralöl (η_{100 Grad Celsius} = 3,9 qmm/s)
24,08 g  Methacrylsäureester eines C12-C15-Alkoholgemisches mit 23 % verzweigten Alkoholen
9,22 g  Methacrylsäureester eines unverzweigten C16-C18-Alkoholgemisches
0,13 g  Dodecylmercaptan
0,36 g  tert.-Butylperoctoat

Zulauf:

482,02 g  Methacrylsäureester eines C12-C15-Alkoholgemisches mit 23 % verzweigten Alkoholen
184,68 g  Methacrylsäureester eines unverzweigten C16-C18-Alkoholgemisches
2,67 g  Dodecylmercaptan
2,00 g  tert.-Butylperoctoat

Polymerisatgehalt = 70 %
Viskosität (100 Grad Celsius, 70 Gew.-%ig) = 560 qmm/s Zusammensetzung:

• 0 Mol-% a)
• 24 Mol-% b)
• 76 Mol-% c)

   davon 59 Mol-%, die als unverzweigte C4-C15-Alkylmethacrlate zu klassieren sind.

Production as additive A, but

Template:

300 g mineral oil (η _{100 degrees Celsius} = 3.9 qmm / s)
24.08 g of methacrylic acid ester of a C12-C15 alcohol mixture with 23% branched alcohols
9.22 g of methacrylic acid ester of an unbranched C16-C18 alcohol mixture
0.13 g dodecyl mercaptan
0.36 g of tert-butyl peroctoate

Intake:

482.02 g of methacrylic acid ester of a C12-C15 alcohol mixture with 23% branched alcohols
184.68 g of methacrylic acid ester of an unbranched C16-C18 alcohol mixture
2.67 g dodecyl mercaptan
2.00 g of tert-butyl peroctoate

Polymer content = 70%
Viscosity (100 degrees Celsius, 70% by weight) = 560 qmm / s Composition:

• 0 mol% a)
• 24 mol% b)
• 76 mol% c)

59 mol% of which are classified as unbranched C4-C15-alkyl methacrylates.

Comparative Example 5 Additive B

Vorlage:

300 g  Mineralöl (η₁₀₀ Grad C = 3,9 qmm/s)
25,8 g  Methacrylsäureester eines C₁₂-C₁₅-Alkoholgemisches mit 23 % verzweigten Alkoholen
7,5 g  Methacrylsäureester eines unverzweigten C₁₆-C₁₈-Alkoholgemisches
0,13 g  Dodecylmercaptan
0,36 g  tert.-Butylperoctoat

Zulauf:

517,4 g  Methacrylsäure eines C₁₂-C₁₅-Alkoholgemisches mit verzweigten Alkoholen
149,3 g  Methacrylsäureester eines unverzweigten C₁₆-C₁₈-Alkoholgemisches
2,67 g  Dodecylmercaptan
2,0 g  tert.-Butylperoctoat

Polymerisatgehalt = 70 %
Viskosität (100 Grad C, 70 Gew.-%ig) = 560 qmm/s Zusammensetzung:

• 0 Mol-% a)
• 20 Mol-% b)
• 79 Mol-% c)

   davon 62 Mol-%, die als unverzweigte C₄-C₁₅-Alkylmethacrylate zu klassieren sind.

Production as additive A, but

Template:

300 g mineral oil (η ₁₀₀ degrees C = 3.9 qmm / s)
25.8 g of methacrylic acid ester of a C ₁₂ -C ₁₅ alcohol mixture with 23% branched alcohols
7.5 g of methacrylic acid ester of an unbranched C ₁₆ -C ₁₈ alcohol mixture
0.13 g dodecyl mercaptan
0.36 g of tert-butyl peroctoate

Intake:

517.4 g of methacrylic acid of a C ₁₂ -C ₁₅ alcohol mixture with branched alcohols
149.3 g of methacrylic acid ester of an unbranched C ₁₆ -C ₁₈ alcohol mixture
2.67 g dodecyl mercaptan
2.0 g of tert-butyl peroctoate

Polymer content = 70%
Viscosity (100 degrees C, 70% by weight) = 560 qmm / s Composition:

• 0 mol% a)
• 20 mol% b)
• 79 mol% c)

62 mol% of which are classified as unbranched C ₄ -C ₁₅ -alkyl methacrylates.

Claims (1)

1. Use of polymethacrylates P as oil additives, the polymethacrylates P being in the form of random copolymers and synthesised from

   a) 10 - 30 mol.% of methyl methacrylate

   b) 10 - 70 mol.% of alkyl methacrylates with unbranched alkyl groups having 16 to 30 carbon atoms in the alkyl group,

   c) 80 - 0 mol.% of alkyl methacrylates with unbranched alkyl groups having 4 to 15 carbon atoms and/or branched alkyl groups having 4 to 40 carbon atoms in the alkyl group as the monomer component,

      characterised in that the polyalkyl methacrylates P are used in amounts between 0.05 and 1 wt.% as pour point improving agent in mineral oils, with the proviso that the monomer component b) comprises several alkyl methacrylates which are different from one another.