EP0140274B2 - Lubricating oil additives - Google Patents

Description

Field of the Invention

The invention relates to multifunctional lubricating oil additives based on polyalkyl acrylates and polyalkyl methacrylates as well as systems formed from olefin copolymers (OCP) or hydrogenated styrene-diene copolymers (HSD) and PAMA. To improve the "pour point", the viscosity / temperature behavior at high and low temperatures and, if necessary, the dispersing / detergent properties.

State of the art

Lubricating oils generally contain n-paraffin hydrocarbons, which on the one hand have a positive 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 ("sticking"). 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 performs a partial dewaxing of the oils up to a pour point in the range of -15 ° C. and makes use of the further reduction Pour point (down to about -40 ° C) so-called pour point depressants, which effectively reduce the pour point even 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.

The currently preferred pour point depressants are polymethacrylates, which lower the pour point of lubricating oils sufficiently in a concentration 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 branching wheel between 10 and 30 mol%. Polymethacrylates in the M range between approx. 5,000 and 500,000 are available, which allow the flow behavior of light, low-molecular to heavy, high-molecular lubricating oils to be improved.

FR-A 2 407 259 has set itself the task of the pour point of a so-called non-classic oil, namely a hydrocracked base oil with a particularly high V.I. (XHVI-ÖI with V.I. of at least 140 according to ASTM D-2270). Such oils are not special cases directly comparable to "classic" oils. thereby proving that polyalkyl methacrylates with an average carbon number of 12.4-13.7 in the range of the C9-C18 alkyl esters and at least 6 alkyl chains with a different C number in the range of the alkyl esters with 9-18 carbon atoms, which are especially for HVI oils were developed according to which FR-A did not produce any useful results with these non-classical oils.

task

In addition to reducing the pour point, multifunctional additives for mineral oils are also said to improve the viscosity / temperature behavior at high and low temperatures. This requires, compared to pure pour point improvers, larger additional amounts in the range between 1-30% by weight. In addition, such multifunctional viscosity index improvers (VI improvers) can also have dispersing / detergent properties (cf. Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 20, loc.cit., Pp. 457-671) . These multifunctional VI improvers are mostly based on polymethacrylic acid esters (PAMA) and combinations (mixed polymers) of PAMA with olefin copolymers (OCP) or hydrogenated styrene-diene copolymers (HSD) and less on the basis of OCP or HSD alone.

The object on which the present invention is based relates to improving the viscosity / temperature behavior of mineral oils containing n-paraffin in the broadest sense, especially at low temperatures, caused by the tendency of the n-paraffins to crystallize. This task in one of its particularly acute forms is explained in more detail using the example of lubricating oils containing n-paraffin: As is well known, the exhaustion of existing oil deposits has led to the exploitation of less-efficient or lower-quality oil deposits. There is therefore an increasing amount of quality poorer mineral oils (base oils). For example, the fact that these oils are less and less dewaxed and are more difficult to handle technologically can have a critical impact; (so-called "critical base oils"). There was therefore a need for pour-point or flow-improving additives for mineral oils, which also facilitate the recycling of technologically difficult to handle mineral oils. The problems shown above are overlaid by special application problems. For motor multigrade oils that contain OCP as a VI improver, there are increased difficulties with regard to the pour point, since the OCP's obviously have a negative effect on the pour point. Difficulties are also observed when using OCP-containing lubricating oils in diesel engines, namely when diesel fuel gets into OCP-containing engine oils. Despite the thinning that occurs, the pour point usually rises under the influence of the diesel fuel. The funds available could only incompletely meet the new technical requirements.

solution

• I. 10-99 Gew.-% eines oder mehrerer Polymeren P₁, die
  • a) aus Estern der Methacryl-, der Acrylsäure oder beiden mit geradkettigen, unverzweigten Alkoholen mit mindestens 6 und höchstens 15 Kohlenstoffatomen und
  • b) aus Estern der Methacryl-, der Acrylsäure oder beiden mit geradkettigen unverzweigten Alkoholen mit 16 bis 30 Kohlenstoffatomen und
  • c) aus Estern der Methacryl-, der Acrylsäure oder beiden mit verzweigten Alkoholen mit 8 bis 40 Kohlenstoffatomen,
  • d) aus Estern der Methacryl-, der Acrylsäure oder beiden mitAlkoholem mit 1 bis 5 Kohlenstoffatomen,
  • e) aus radikalisch copolymerisierbaren Monomeren, die funktionelle Gruppen im Molekül aufweisen, aufgebaut sind,
    wobei der Anteil des Bestandteils a) 10-100 Mol-%, der Anteil des Bestandteils b) 0-5 Mol-%, vorzugsweise 0,5-5 Mol-%, speziell 1-5 Mol-%, der Anteil des Bestandteils c) 0-90 Mol-%, vorzugsweise 0,5-90 Mol-%, besonders bevorzugt 0,5-60 Mol-%, der Anteil des Bestandteils d) 0-50 Mol-%, vorzugsweise 5-30 Mol-% und der Anteil des Bestandteils e) 0-20 Mol-%, vorzugsweise 2-15 Mol-%, jeweils bezogen auf das Polymere P₁ ausmacht, und
• II. 90-1 Gew.-% eines oder mehrerer Polymerer P₂, die
  • a') aus Estern der Methacryl-, der Acrylsäure oder beiden mit geradkettigen unverzweigten Alkoholen mit mindestens 6 und höchstens 15 Kohlenstoffatomen und
  • b') aus Estern der Methacryl-, der Acrylsäure oder beiden mit geradkettigen, unverzweigten Alkoholen mit 16 bis 30 Kohlenstoffatomen und
  • c') aus Estern der Methacryl-, der Acrylsäure oder beiden mit verzweigten Alkoholen mit 8 bis 40 Kohlenstoffatomen und
  • d') aus Estern der Methacryl-, der Acrylsäure oder beiden mit Alkoholen mit 1 bis 5 Kohlenstoffatomen, e') aus radikalisch copolymerisierbaren Monomeren, die funktionelle Gruppen im Molekül aufweisen, aufgebaut sind,
  
  wobei der Anteil des Bestandteils a') 30-90 Mol.-%, der Anteil des Bestandteils b') 10-70 Mol.-%, der Antei des Bestandteils c') 0-90 Mol.-%, vozugsweise 10-90 Mol.-%, besonders bevorzugt 10-30 Mol.- %, und der Anteil des Bestandteils d') 0-50 Mol.-%, vorzugsweise 5-30 Mol.-%, und der Anteil des Bestandteils e') 0-20 Mol-%, vorzugsweise 2-15 Mol.-%, jeweils bezogen auf das Polymerisat P₂ ausmacht, und einer zweiten Polymerkomponente, ausgewählt aus der Gruppe der VI-verbessernden Olefincopolymerisate mit der Maßgabe, daß die Olefincopolymerisate aus Ethylen, Propylen, Butylen oder Isobutylen aufgebaut sind, auf welche Monomeren aus der Gruppe der Bestandteile a), b), c) gepfropft wurden, oder in Form einer konzentrierten Polymeremulsion, die als kontinuierliche Phase Poly(meth)acrylate, ein Trägermedium, das gegenüber den Poly(meth)acrylestern als gutes Lösungsmitel gegenüber den Olefincopolymerisaten aufgrund des Gehalts an Poly(meth)acrylsäureester als weniger gutes Lösungsmittel wirkt und als Stabilisator für die Phasenverteilung ein Pfropf- oder ein Blockpolymerisat aus Olefincopolymerisaten und (Meth)acrylsäure-estern enthält, neben dem Lösungsmittel L ausgewählt aus der Gruppe bestehend aus paraffin- oder naphthenbasischen Mineralölen, Esterölen oder Poly-a-Olefinen enthalten. Mit der Maßgabe, daß an Anteil der Polymeren (P) und der Olefincopolymerisate 20-80 Gew.-%, bezogen auf die Additive beträgt.

It has now been found that additives can be adapted to the paraffin content of the lubricating oils and thus enable the problem to be solved which, in addition to the customary solvents, mixtures of the polymers (P) which

• I. 10-99 wt .-% of one or more polymers P ₁ , the
  • a) from esters of methacrylic acid, acrylic acid or both with straight-chain, unbranched alcohols having at least 6 and at most 15 carbon atoms and
  • b) from esters of methacrylic acid, acrylic acid or both with straight-chain unbranched alcohols having 16 to 30 carbon atoms and
  • c) from esters of methacrylic acid, acrylic acid or both with branched alcohols having 8 to 40 carbon atoms,
  • d) from esters of methacrylic acid, acrylic acid or both with alcohols having 1 to 5 carbon atoms,
  • e) are built up from free-radically copolymerizable monomers which have functional groups in the molecule,
    wherein the proportion of component a) 10-100 mol%, the proportion of component b) 0-5 mol%, preferably 0.5-5 mol%, especially 1-5 mol%, the proportion of component c ) 0-90 mol%, preferably 0.5-90 mol%, particularly preferably 0.5-60 mol%, the proportion of component d) 0-50 mol%, preferably 5-30 mol% and the proportion of component e) is 0-20 mol%, preferably 2-15 mol%, in each case based on the polymer P ₁ , and
• II. 90-1 wt .-% of one or more polymers P ₂ , the
  • a ') from esters of methacrylic acid, acrylic acid or both with straight-chain unbranched alcohols having at least 6 and at most 15 carbon atoms and
  • b ') from esters of methacrylic acid, acrylic acid or both with straight-chain, unbranched alcohols having 16 to 30 carbon atoms and
  • c ') from esters of methacrylic acid, acrylic acid or both with branched alcohols having 8 to 40 carbon atoms and
  • d ') from esters of methacrylic acid, acrylic acid or both with alcohols having 1 to 5 carbon atoms, e') from free-radically copolymerizable monomers which have functional groups in the molecule,
  
  wherein the proportion of component a ') 30-90 mol%, the proportion of component b') 10-70 mol%, the proportion of component c ') 0-90 mol%, preferably 10-90 Mol%, particularly preferably 10-30 mol%, and the proportion of component d ') 0-50 mol%, preferably 5-30 mol%, and the proportion of component e') 0- 20 mol%, preferably 2-15 mol%, each based on the polymer P ₂ , and a second polymer component selected from the group of VI-improving olefin copolymers, with the proviso that the olefin copolymers from ethylene, propylene, butylene or isobutylene, onto which monomers from the group of constituents a), b), c) have been grafted, or in the form of a concentrated polymer emulsion which, as a continuous phase, comprises poly (meth) acrylates, a carrier medium which is opposite the poly (meth ) acrylic esters as a good solvent compared to the olefin copolymers because of the content of poly (meth) acrylic acid ester as a less good solution acts medium and contains as a stabilizer for the phase distribution a graft or a block polymer from olefin copolymers and (meth) acrylic esters, in addition to the solvent L selected from the group consisting of paraffin or naphthenic mineral oils, ester oils or poly-a-olefins. With the proviso that the proportion of the polymers (P) and the olefin copolymers is 20-80% by weight, based on the additives.

(The sum of ae and a'-e 'is 100 mol%).

Lubricating oils in the sense of the present invention are understood to mean paraffin-based and naphthenic-based vacuum distillate oils.

It should be emphasized that, in addition to the solvents, the additives according to the invention also contain VI-improving polyolefins / olefin copolymers (OCP), preferably of the type of the combination of polyalkyl (meth) acrylates (PAMA) and OCP (mixed polymers) as described in DE-PS 29 05 954 or US Pat. No. 4,290,925 is described.

The proportion of the olefin copolymers or the polymers according to the cited DE-PS 29 05 954 or US Pat. No. 4,290,925 in the additives can be 10-70% by weight.

The proportion of the polymers (P) in the additives according to the invention is 10-80% by weight, the total content of polymers is 20-80% by weight.

The proportion of component a) in the polymer P ₁ is preferably 50-100 mol%, especially 100 mol%. The proportion of component b ') in the polymer P ₂ is preferably 20-40 mol%.

Also preferred is the embodiment in which the polymer P ₂ is composed only of components a ') and b').

The following applies equally to components a) and a '): Acrylic or. Methacrylic acid esters with straight-chain unbranched C ₁₀ -C ₁₄ alcohols, for example prepared by the Ziegler process by hydrolysis of aluminum alkoxides. Examples include the Lorole® products from Henkel KG. Düsseldorf and Alfole®, products from Condea, Hamburg).

It applies to components b) and b ') that they are preferably acrylic or methacrylic acid esters of straight-chain, unbranched C ₁₆ -C ₂₄ alcohols, especially C ₁₈ -C ₂₂ alcohols. The tallow fatty alcohols and Alfole® (products from Condea) may be mentioned.

For components c) and c ') it applies that it preferably consists of esters of acrylic or methacrylic acid with branched C ₈ -C ₂₀ alcohols of the isoalkanol type, in particular of isodecyl, isotridecyl and isooctodecyl alcohols.

The molecular weights Mw of the polymers P ₁ are generally in the range from 50,000 to 500,000, and those of the polymers P ₂ in the range from 50,000 to 500,000.

The polymers P ₁ and P ₂ can be prepared by the customary free-radical polymerization processes.

worin R₁ Wasserstoff oder Methyl und Bs einen (inerten) heterocyclischen 5-oder6-gliedrigen Ring oder einen Rest

bedeutet, wobei Z für Sauerstoff oder einen Rest -NR₄ und Q für eine gegebenenfalls alkylierte Kohlenwasserstoffbrücke mit insgesamt 2 bis 10 Kohlenstoffatomen und R₂ und R₃ jeweils für einen Alkylrest mit 1 bis 6 Kohlenstoffatomen stehen oder zusammen unter Einbeziehung des Stickstoffs und gegebenenfalls anderer Heteroatome einen heterocyclischen 5- oder 6-gliedrigen Ring bilden können und worin R₄ für Wasserstoff oder einen Alkylrest mit 1 bis 6 Kohlenstoffatomen steht.Component e) of the polymers P _{1 is} by definition understood to mean free-radically polymerizable monomers with functional groups in the molecule, in particular those whose positive effect on oil additives in the sense of dispersing or detergent activity is known. For example, compounds of the general formula may be mentioned

wherein R _{1 is} hydrogen or methyl and Bs is an (inert) heterocyclic 5- or 6-membered ring or a radical

means, where Z is oxygen or a radical -NR ₄ and Q are an optionally alkylated hydrocarbon bridge with a total of 2 to 10 carbon atoms and R ₂ and R _{3 are} each an alkyl radical with 1 to 6 carbon atoms or together including nitrogen and optionally others Heteroatoms can form a heterocyclic 5- or 6-membered ring and in which R _{4 represents} hydrogen or an alkyl radical having 1 to 6 carbon atoms.

Examples include C- and N-vinylpyridine-, vinylpyrrolidone, vinylcarbazole, vinylimidazole and their alkyl derivatives, in particular the N-vinyl compounds, also the dialkylaminoalkyl esters of (meth) acrylic acid, especially dimethylaminoethyl acrylate and methacrylate, dimethylaminopropylacrylate, methacrylate and the corresponding amide (methacrylate) - or -methacrylamides) such as dimethylaminopropyl (meth) acrylamide. The above definitions (formula I) also apply to e ') in the polymer P ₂ .

The solvents (L) used in the additives according to the invention are the paraffin- or naphthene-based mineral oils known in the art for lubricating oil additives or the known ester oils or poly-a-olefins. (See Ullmanns Encyklopadie der techn. Chemie, Volume 20, loc.cit., Pp. 483-529).

Preparation of the polymers P ₁ and P ₂

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), c), d) and e) is placed in a reaction vessel which is suitably equipped with a stirrer, thermometer, reflux condenser and metering line.

The mixture is heated to about 90-100 ° C. under a CO ₂ atmosphere and with 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), c), d) and e) and further initiator are metered in; approx. 2 hours after the end of the feed, further initiator is fed. The total amount of initiator is generally 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. (The production of the second polymer component of the type of combination of polyalkyl (meth) acrylates (PAMA) and OCP is carried out according to DE-PS 29 05 954 and US-PS 4,290,925.)

Preparation of the polymer mixtures from P ₁ and P ₂

You can do this as follows:

One component is placed in a suitable container and heated to approx. 80-120 ° C with stirring. The admixing components are also heated to approx. 80-120 ° C and metered in as quickly as possible to the component while stirring.

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

The additive according to the invention, possibly together with other additives, such as DI package and OCP-VI improver, is dissolved in the base oil at 50-60 ° C. with stirring.

Use of additives

The additives according to the invention can be added to the lubricating oils in a manner known per se.

For engine lubricating oils and ATF oils, an addition of 1-10% by weight, preferably 2-6% by weight is recommended; for hydraulic and gear oils, an addition of 5-30% by weight, preferably 10- 20% by weight, recommended.

Advantageous effects of the invention lie in the flexible adaptation to any special base oil, especially critical base oils and when using OCP. Oil formulations containing the additives according to the invention, in addition to the required viscosity data at 100 ° C., show very favorable values for pour point and stable pour point as well as excellent viscosity data at -15 ° C. to 40 ° C.

Pour Stability (Stable Pourpoint: Fed. Test. Meth. 203 Std.Nr. 791/Cycle C

Characterization can be carried out using the following measured variables:

Pour Stability (Stable Pourpoint: Fed. Test. Meth. 203 hours No. 791 / Cycle C

Production of oil additives Additive A

• 252 g Mineralöl (η_100°C=5.3 mm²/s)
• 26,6 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 1,4 g Methylmethacrylat
• 1,6 g tert.-Butylperoctoat

The following mixture is placed in a 1 1 four-necked flask with stirrer, thermometer, reflux condenser and metering line:

• 252 g mineral oil (η _{100 ° C} = 5.3 mm ² / s)
• 26.6 g methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 1.4 g methyl methacrylate
• 1.6 g of tert-butyl peroctoate

• 304 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 16 g Methylmethacrylat
• 2,56 g tert.-Butylperoctoat

After the components have been dissolved, the mixture below is uniformly metered in over a period of 210 minutes.

• 304 g of methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 16 g methyl methacrylate
• 2.56 g of tert-butyl peroctoate

• Polymerisatgehalt=58 Gew.-%
• Viskosität (100°C, 58 Gew.-%ig)=500 mm²/s
• Viskosität (100°C, 5,8 Gew.-%ig in Mineralöl mit η_100°C=5,3 mm²/s)=11,0 mm²/s SS!¹> (5,8 Gew.-% ig in Mineralöl mit η_100°C=5,3 mm²/s)=7,5

Two hours after the end of the feed, 0.7 g of tert-butyl peroctoate are added. Total polymerization time 8 hours. A clear, viscous solution is obtained.

• Polymer content = 58% by weight
• Viscosity (100 ° C, 58% by weight) = 500 mm ² / s
• Viscosity (100 ° C, 5.8% by weight in mineral oil with η _{100 ° C} = 5.3 mm ² / s) = 11.0 mm ² / s SS! ¹ > (5.8% by weight in mineral oil with η _{100 ° C} = 5.3 mm ² / s) = 7.5

Additive B Manufacture and data like additive A, however

• 252 g Mineralöl (_η100°C=5,3 mm²/s)
• 6,2 g Methacrylsäureester eines n-C₁₆-C₁₈-Alkoholgemisches
• 20,4 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 1,4 g Methacrylsäuremethylester
• 1,6 g tert.-Butylperoctoat

Template:

• 252 g mineral oil ( _{η100 ° C} = 5.3 mm ² / s)
• 6.2 g of methacrylic acid ester of an nC ₁₆ -C ₁₈ alcohol mixture
• 20.4 g of methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 1.4 g of methyl methacrylate
• 1.6 g of tert-butyl peroctoate

• 71 g Methacrylsäureester eines n-C₁₆-C₁₈-Alkoholgemisches
• 233 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 16 g Methylmethacrylat
• 2,56 g tert.-Butylperoctoat

Intake:

• 71 g of methacrylic acid ester of an nC ₁₆ -C ₁₈ alcohol mixture
• 233 g of methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 16 g methyl methacrylate
• 2.56 g of tert-butyl peroctoate

Additive C Manufacture and data like additive A, however

• 252 g Mineralöl (_η100°C=5,3 mm²/s)
• 6,75 g Methacrylsäureester eines n-C,₈-C₂₂-Alkoholgemisches
• 19,85 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 1,4 g Methylmethacrylat
• 1,6 g tert.-Butylperoctoat

Template:

• 252 g mineral oil ( _{η100 ° C} = 5.3 mm ² / s)
• 6.75 g of methacrylic acid ester of an nC, ₈ -C ₂₂ alcohol mixture
• 19.85 g of methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 1.4 g methyl methacrylate
• 1.6 g of tert-butyl peroctoate

• 77,2 g Methacrylsäureester eines n-C₁₂-C₂₂-Alkoholgemisches
• 226,8 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 16 g Methacrylsäuremethylester
• 2,56 g tert.-Butylperoctoat

Intake:

• 77.2 g methacrylic acid ester of an nC ₁₂ -C ₂₂ alcohol mixture
• 226.8 g of methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 16 g of methyl methacrylate
• 2.56 g of tert-butyl peroctoate

Additive D Production as additive A, but

• 252 g Mineralöl (η_100°C=5,3 mm²/s)
• 26,6 g Methacrylsäureester eines iso-C₁₀-Alkohols
• 1,4 g Methylmethacrylat
• 1,6 g tert.-Butylperoctoat

Template:

• 252 g mineral oil (η _{100 ° C} = 5.3 mm ² / s)
• 26.6 g of methacrylic acid ester of an iso-C ₁₀ alcohol
• 1.4 g methyl methacrylate
• 1.6 g of tert-butyl peroctoate

• 304 g Methacrylsäureester eines iso-C₁₀-Alkohols
• 16 g Methylmethacrylat
• 2,56 g tert.-Butylperoctoat

Intake:

• 304 g of methacrylic acid ester of an iso-C ₁₀ alcohol
• 16 g methyl methacrylate
• 2.56 g of tert-butyl peroctoate

• Polymerisatgehalt=58 Gew.-%

A clear, viscous solution is obtained.

• Polymer content = 58% by weight

• Viskosität (100°C, 58 Gew.-%ig)=1000 mm²/s
• Viskosität (100°C, 5,8 Gew.-%ig in Mineralöl mit η_100°C=5,3 mm²/s=11,0 mm²/s
• SSI¹⁾ (58 Gew.-%ig in Mineralöl mit η_100°C=5,3 mm²/S)=7,5

¹⁾ SSI = shear stability index = loss of thickening effect in% with shear stability test according to DIN 51 382

• Viscosity (100 ° C, 58% by weight) = 1000 mm ² / s
• Viscosity (100 ° C, 5.8% by weight in mineral oil with η _{100 ° C} = 5.3 mm ² / s = 11.0 mm ² / s
• SSI ¹⁾ (58% by weight in mineral oil with η _{100 ° C} = 5.3 mm ² / S) = 7.5

Additive E Manufacture and data like additive A, however

• 252 g Mineralöl (_η100°C=5,3 mm²/s)
• 11,76 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 14,84 g Methacrylsäureester eines iso-C₁₈-Alkohols
• 1,4 g Methylmethacrylat
• 1,6 g tert.-Butylperoctoat

Template:

• 252 g mineral oil ( _{η100 ° C} = 5.3 mm ² / s)
• 11.76 g of methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 14.84 g of methacrylic acid ester of an iso-C ₁₈ alcohol
• 1.4 g methyl methacrylate
• 1.6 g of tert-butyl peroctoate

• 134,4 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 169,6 g Methacrylsäureester eines iso-C₁₈-Alkohols
• 16,0 g Methylmethacrylat
• 2,56 tert.-Butylperoctoat

Intake:

• 134.4 g methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 169.6 g of methacrylic acid ester of an iso-C ₁₈ alcohol
• 16.0 g methyl methacrylate
• 2.56 tert-butyl peroctoate

Additive F Equipment as for additive A

• 252 g Mineralöl (_η100°C=5,3 mm²/s)
• 26,6 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 1,4 g Methmethacrylat
• 1,6 g tert.-Butylperoctoat

Template:

• 252 g mineral oil ( _{η100 ° C} = 5.3 mm ² / s)
• 26.6 g methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 1.4 g meth methacrylate
• 1.6 g of tert-butyl peroctoate

• 152,9 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 8,1 g Methylmethacrylat
• 1,29 g tert.-Butylperoctoat

Inlet 1:

• 152.9 g of methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 8.1 g methyl methacrylate
• 1.29 g of tert-butyl peroctoate

Feed 1 is metered in uniformly within 210 minutes. 120 minutes after the end of the inlet, inlet 2 is started:

• 151,1 g Methacrylsäureester eines iso-C₁₀-Alkohols
• 7,9 g Methylmethacrylat
• 1,27 g tert.-Butylperoctoat

Inlet 2:

• 151.1 g of methacrylic acid ester of an iso-C ₁₀ alcohol
• 7.9 g methyl methacrylate
• 1.27 g of tert-butyl peroctoate

Two hours after the end of feed 2, 0.7 g of tert-butyl peroctoate is added. Total polymerization time is 12 hours.

• Polymerisatgehalt=58 Gew.-%ig
• Viskosität (100°C 58 Gew.-%ig)=800 mm²/s
• Viskosität (100°C, 5,8 Gew.-% in Mineralöl mit η_100°C=5,3 mm²/s)=11,0 mm²/s
• SSI¹⁾ (5,8 % ig in Mineralöl mit η_100°C =5,3 mm²/s)=7,5

A slightly cloudy, viscous solution is obtained.

• Polymer content = 58% by weight
• Viscosity (100 ° C 58% by weight) = 800 mm ² / s
• Viscosity (100 ° C, 5.8% by weight in mineral oil with η _{100 ° C} = 5.3 mm ² / s) = 11.0 mm ² / s
• SSI ¹⁾ (5.8% in mineral oil with η _{100 ° C} = 5.3 mm ² / s) = 7.5

Additive G

• 17,4 g eines Copolymerisats, bestehend aus 70 Gew.-% Äthylen und 30 Gew.-% Propylen mit Mw=80 000
• 252 g Mineralöl (η_100°C=5,3 mm²/s)

In a 1 liter four-necked flask with stirrer, thermometer, reflux condenser and metering line are placed.

• 17.4 g of a copolymer consisting of 70% by weight of ethylene and 30% by weight of propylene with Mw = 80,000
• 252 g mineral oil (η _{100 ° C} = 5.3 mm ² / s)

• ¹⁾ SSI=Scherstabilitätsindex=Verlust an Verdickungswirkung in % bei Scherstabilitätsprüfung nach DIN 51 382
• ¹⁾ SSI=Scherstabilitätsindex=Verlust an Verdickungswirkung in % bei Scherstabilitätsprüfung nach DIN 51 382

• 28,4 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 1,5 g Methylmethacrylat
• 1,0 g tert.-Butylperoctoat

After the copolymer has been dissolved within 10 hours at 90 ° C., the following mixture is added:

• ¹⁾ SSI = shear stability index = loss of thickening effect in% with shear stability test according to DIN 51 382
• ¹⁾ SSI = shear stability index = loss of thickening effect in% with shear stability test according to DIN 51 382

• 28.4 g methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 1.5 g methyl methacrylate
• 1.0 g of tert-butyl peroctoate

• 285,7 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 15,0 g Methylmethacrylat
• 1,5 g tert.-Butylperoctoat

After dissolving the components introduced, the mixture below is metered in uniformly over a period of 210 minutes at 90 ° C.

• 285.7 g of methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 15.0 g methyl methacrylate
• 1.5 g of tert-butyl peroctoate

• 7,8 Mineralöl (η100°C=5.3 mm²/s)
• 10,76 g N-Vinylpyrrolidon-2

zugesetzt und die Temperatur auf 130°C erhöht. Jetzt werden

• 0,9 g tert.-Butylperbenzoat

zugegeben.

• Nach 1 bzw. 2 Stunden wird mit je
• 0,4 g tert.-Butylperbenzoat nachgefüttert.
• Der Versuch wird noch weitere 5 Stunden bei 130°C gehalten. Es wird eine trübe viskose Lösung erhalten.
• Polymerisatgehalt: 58 Gew.-%
• Viskosität (100°C, 58 Gew.-%ig)=2000 mm²/s
• Viskosität (100°C, 5,8 Gew.-%ig in Mineralöl mit η_100°C=5,3 mm²/s)=17,0 mm²/s
• SSI¹⁾ 5,8 Gew.-% ig in Mineralöl mit η100°C=5,3 mm²/s)=32

2 hours after the end of the feed, 0.66 g of tert-butyl peroctoate is added. After a total polymerization time of 8 hours, the polymer

• 7.8 mineral oil (η100 ° C = 5.3 mm ² / s)
• 10.76 g of N-vinyl pyrrolidone-2

added and the temperature increased to 130 ° C. Now become

• 0.9 g of tert-butyl perbenzoate

admitted.

• After 1 or 2 hours with
• 0.4 g of tert-butyl perbenzoate was fed.
• The experiment is held at 130 ° C. for a further 5 hours. A cloudy, viscous solution is obtained.
• Polymer content: 58% by weight
• Viscosity (100 ° C, 58% by weight) = 2000 mm ² / s
• Viscosity (100 ° C, 5.8% by weight in mineral oil with η _{100 ° C} = 5.3 mm ² / s) = 17.0 mm ² / s
• SSI ¹⁾ 5.8% by weight in mineral oil with η100 ° C = 5.3 mm ² / s) = 32

Additive H

• 258 g Mineralöl (η_100°C=5,3 mm²/s)
• 25,8 g Methacrylsäureesters eines C₁₂-C₁₈-Alkoholgemisches mit 20% iso-Anteilen
• 2,9 g Methylmethacrylat
• 1,2 g tert.-Butylperoctoat

The following are placed in a 1 1 four-necked flask with stirrer, thermometer, reflux condenser and metering line:

• 258 g mineral oil (η _{100 ° C} = 5.3 mm ² / s)
• 25.8 g of methacrylic acid ester of a C ₁₂ -C ₁₈ alcohol mixture with 20% iso shares
• 2.9 g methyl methacrylate
• 1.2 g of tert-butyl peroctoate

• 282 g Methacrylsäureester eines C₁₂-C₁₈-Alkoholgemisches mit 20% iso-Anteilen
• 31,3 g Methylmethacrylat
• 1,9 g tert.-Butylperoctoat

After the components have been dissolved, the following mixture is metered in at 90 ° C. over a period of 210 minutes:

• 282 g of methacrylic acid ester of a C ₁₂ -C ₁₈ alcohol mixture with 20% iso shares
• 31.3 g methyl methacrylate
• 1.9 g of tert-butyl peroctoate

• 7,97 g Mineralöl (_η100°C=5,3 mm²/s)
• 10,57 g N-Vinylpyrrolidon-2

und die Temperatur wird auf 130°C erhöht.Two hours after the end of the feed, 0.7 g of tert-butyl peroctoate are added and the mixture is stirred at 90 ° C. for a further 5 hours. Then add:

• 7.97 g mineral oil ( _{η100 ° C} = 5.3 mm ² / s)
• 10.57 g of N-vinyl pyrrolidone-2

and the temperature is raised to 130 ° C.

• 0,9 g tert.-Butylperbenzoat

Now add:

• 0.9 g of tert-butyl perbenzoate

After a further 1 or 2 hours, 0.4 g of tert-butyl perbenzoate are added and the mixture is then stirred at 130 ° C. for 5 hours.

• Polymerisatgehalt=57 Gew.-%
• Viskosität (100°C, 57 Gew.-%ig)=1300 mm²/s
• Viskosität (100°C, 5,7 Gew.-%ig in Mineralöl mit η_100°C=5,3 mm²/s)=14,4 mm²/s
• SSI¹⁾ (5,7 Gew.-%ig in Mineralöl mit _η100°C=5,3 mm²/s)=24

A clear, viscous solution is obtained.

• Polymer content = 57% by weight
• Viscosity (100 ° C, 57% by weight) = 1300 mm ² / s
• Viscosity (100 ° C, 5.7% by weight in mineral oil with η _{100 ° C} = 5.3 mm ² / s) = 14.4 mm ² / s
• SSI ¹⁾ (5.7% by weight in mineral oil with _{η100 ° C} = 5.3 mm ² / s) = 24

Additive J Manufacture and data like additive A, however

• 252 g Mineralöl (η_100°C=5,3 mm²/s)

• 1) SSI=Scherstabilitätsindex=Verlust an Verdickungswirkung in % bei Scherstabilitätsprüfung nach DIN 51 382
• ¹⁾ SSI=Scherstabilitätsindex=Verlust an Verdickungswirkung in % bei Scherstabilitätsprüfung nach DIN 51 382

• 28 g Methacrylsäureester eines C₁₂-C₁₈-Alkoholgemisches mit 13% iso-Anteilen
• 1,6 g tert.-Butylperoctoat

Template:

• 252 g mineral oil (η _{100 ° C} = 5.3 mm ² / s)

• 1) SSI = shear stability index = loss of thickening effect in% with shear stability test according to DIN 51 382
• ¹⁾ SSI = shear stability index = loss of thickening effect in% with shear stability test according to DIN 51 382

• 28 g methacrylic acid ester of a C ₁₂ -C ₁₈ alcohol mixture with 13% iso shares
• 1.6 g of tert-butyl peroctoate

• 320 g Methacrylsäureester eines C₁₂-C₁₈-Alkoholgemisches mit 13% iso-Anteilen
• 2,56 g tert.-Butylperoctoat

Intake:

• 320 g of methacrylic acid ester of a C ₁₂ -C ₁₈ alcohol mixture with 13% iso shares
• 2.56 g of tert-butyl peroctoate

Additive K Manufacture and data like additive A, however

• 252 g Mineralöl (η_100°C=5,3 mm²/s)
• 11,7 g Methacrylsäureester eines n-C₁₆-C₁₈-Alkoholgemisches
• 14,9 g Methacrylsäureester eines iso-C₁₀-Alkohols
• 1,4 g Methylmethacrylat
• 1,6 g tert.-Butylperoctoat

Template:

• 252 g mineral oil (η _{100 ° C} = 5.3 mm ² / s)
• 11.7 g of methacrylic acid ester of an nC ₁₆ -C ₁₈ alcohol mixture
• 14.9 g of methacrylic acid ester of an iso-C ₁₀ alcohol
• 1.4 g methyl methacrylate
• 1.6 g of tert-butyl peroctoate

• 133,4 g Methacrylsäureester eines n-C₁₆-C₁₈-Alkoholgemisches
• 170,6 g Methacrylsäureester eines iso-C₁₀-Alkohols
• 16,0 g Methmethacrylat
• 2,56 g tert.-Butylperoctoat

Intake:

• 133.4 g of methacrylic acid ester of an nC ₁₆ -C ₁₈ alcohol mixture
• 170.6 g of methacrylic acid ester of an iso-C ₁₀ alcohol
• 16.0 g meth methacrylate
• 2.56 g of tert-butyl peroctoate

Additive L

• 17,4 g eines Copolymerisats, bestehend aus 70 Gew.-% Äthylen und 30 Gew.-% propylen mit Mw=80 000
• 252 g Mineralöl (η_100°C=5,3 mm²/s)

The following are placed in a 1 liter four-necked flask with stirrer, thermometer, reflux condenser and metering line:

• 17.4 g of a copolymer consisting of 70% by weight of ethylene and 30% by weight of propylene with Mw = 80,000
• 252 g mineral oil (η _{100 ° C} = 5.3 mm ² / s)

• 11,4 g Methacrylsäureester eines n-C₁₆-C₁₈-Alkoholgemisches
• 6,7 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 10,7 g Methacrylsäureester eines iso-C₁₃-Alkohols
• 1,5 Methylmethacrylat
• 1,7 g tert.-Butylperoctoat

After the copolymer has been dissolved within 10 hours at 90 ° C., the following mixture is added:

• 11.4 g of methacrylic acid ester of an nC ₁₆ -C ₁₈ alcohol mixture
• 6.7 g of methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 10.7 g of methacrylic acid ester of an iso-C ₁₃ alcohol
• 1.5 methyl methacrylate
• 1.7 g of tert-butyl peroctoate

• 113,4 g Methacrylsäureester eines n-C₁₆-C₁₈-Alkoholgemisches
• 66,2 g Methacrylsäureester eines n-C₁₂-C₁₄-Alkoholgemisches
• 106,1 g Methacrylsäureester eines iso-C₁₃-Alkohols
• 15,0 g Methylmethacrylat
• 2,7 g tert.-Butyloctoat

After dissolving the components, the following mixture is metered in uniformly at 90 ° C. over a period of 210 minutes:

• 113.4 g of methacrylic acid ester of an nC ₁₆ -C ₁₈ alcohol mixture
• 66.2 g methacrylic acid ester of an nC ₁₂ -C ₁₄ alcohol mixture
• 106.1 g of methacrylic acid ester of an iso-C ₁₃ alcohol
• 15.0 g methyl methacrylate
• 2.7 g of tert-butyl octoate

2 hours after the end of the feed, 0.66 g of tert-butyl peroctoate is added.

• 7,8 g Mineralöl (η_100°C=5,3 mm²/s)
• 10,76 g N-Vinylpyrrolidon-2

zugesetzt und die Temperatur auf 130°C erhöht. Jetzt erfolgt die Zugabe von:

• 0,9 g tert.-Butylperbenzoat

After a total polymerization time of 8 hours, the polymer

• 7.8 g mineral oil (η _{100 ° C} = 5.3 mm ² / s)
• 10.76 g of N-vinyl pyrrolidone-2

added and the temperature increased to 130 ° C. Now add:

• 0.9 g of tert-butyl perbenzoate

• 0,4 g tert.-Butylperbenzoat nachgefüttert.

After 1 or 2 hours with

• 0.4 g of tert-butyl perbenzoate was fed.

• Polymerisatgehalt: 58 Gew.-%
• Viskosität (100°C, 58 Gew.-%ig)=1000 mm²/s
• Viskosität (100°C, 5,8 Gew.-%ig in Mineralöl mit η_100°C=5,3 mm²/s)=14,3 mm²/s
• SSI¹⁾ (5,8 Gew.-% ig in Mineralöl mit η_100°C=5,3 mm²/s)=22

The experiment is held at 130 ° C. for a further 5 hours. A cloudy, viscous solution is obtained.

• Polymer content: 58% by weight
• Viscosity (100 ° C, 58% by weight) = 1000 mm ² / s
• Viscosity (100 ° C, 5.8% by weight in mineral oil with η _{100 ° C} = 5.3 mm ² / s) = 14.3 mm ² / s
• SSI ¹⁾ (5.8% by weight in mineral oil with η _{100 ° C} = 5.3 mm ² / s) = 22

¹ ) SSI = shear stability index = loss of thickening effect in% with shear stability test according to DIN 51 382

Result:

The examples show that with the mixtures according to the invention (Examples 1-2), more favorable pour point values were obtained in both base oils than in the prior art (see Comparative Examples 1-16).

Claims (1)

1. Additives for lubricating oils which contain n-paraffin based on polyalkylmethacrylates and acrylates, which can be adapted to suit the paraffin content of the individual lubricating oils, as well as conventional solvents, characterised in that the additives contain mixtures of a first polymer component (P) which are made up of

I. 10-99% by weight of one or more polymers P1 which are synthesized from

a) esters of methacrylic or acrylic acid or both with straight chained, unbranched alcohols having at least 6 and not more than 15 carbon atoms and

b) esters of methacrylic or acrylic acid or both with straight chained, unbranched alcohols having 16 to 30 carbon atoms and

c) esters of methacrylic or acrylic acid or both with branched alcohols having 8 to 40 carbon atoms,

d) esters of methacrylic or acrylic acid or both with alcohols having 1 to 5 carbon atoms,

e) radically copolymerisable monomers containing functional groups in the molecule,

whilst the proportion of the component a) is 10 to 100 Mol-%, the proportion of component b) is 0 - 5 Mol-%, the proportion of component c) is 0 - 90 Mol-%, the proportion of component d) is 0 - 50 Mol- % and the proportion of component e) is 0 - 20 Mol-%, each based on the polymer P1, and

II) 90 - 1% by weight of one or more polymers P2 which are synthesized from

a') esters of methacrylic or acrylic acid or both with straight chained unbranched alcohols having at least 6 and not more than 15 carbon atoms and

b') esters of methacrylic or acrylic acid or both with straight chained unbranched alcohols having 16 to 30 carbon atoms and

c') esters of methacrylic or acrylic acid or both with branched alcohols having 8 to 40 carbon atoms and

d') esters of methacrylic or acrylic acid or both with alcohols having 1 to 5 carbon atoms,

e') radically copolymerisable monomers which have functional groups in the molecule,

whilst the proportion of component a') is 30 - 90 Mol-%, the proportion of component b') is 10 - 70 Mol-%, the proportion of component c') is 0 - 90 Mol-% and the proportion of component d') is 0 - 50 Mol-% and the proportion of component e') is 0 - 20 Mol-%, each based on the polymer P2, and a second polymer component selected from the group of the VI-improving olefin copolymers, with the proviso that the olefin copolymers are synthesized from ethylene, propylene, butylene or isobutylene onto which monomers from the group of components a), b), c) have been grafted, or in the form of a concentrated polymer emulsion which contains as the continuous phase poly(meth)acrylates, a carrier medium which is a good solvent for the poly(meth)acrylic esters but a less good solvent of the olefin copolymers owing to their content of poly(meth)acrylic acid esters, and as a stabiliser for the phase distribution, a graft or block polymer obtained from olefin copolymers and (meth)acrylic acid esters, in addition to the solvent L selected from the group consisting of paraffin- or naphthene-based mineral oils, ester oils or poly-a-olefins, with the proviso that the proportion of polymers (P), the olefin copolymers (OCP) is 20-80% by weight, based on the additive.