DE4025494A1 - SYNTHESIC OILS, WHOLE OR PARTLY FROM OLIGOMERS OR CONSIST OF COOLIGOMERS OF (METH) ACRYLIC ACID ESTERS AND 1-ALKENES - Google Patents

Abstract

The invention relates to synthetic oils containing, in addition to conventional components, 5 to 100% by weight of cooligomers of (meth)acrylates and 1-alkenes, the cooligomers CM being composed of A) 0 - 75% by weight of at least one 1-alkene having 4 to 32 carbon atoms in the molecule, B) 20 - 100% by weight of at least one (meth)acrylate of the formula I <IMAGE> wherein R represents hydrogen or methyl and R1 represents a straight-chain or branched alkyl radical or a cycloalkyl radical having 4 to 32 carbon atoms in the alkyl radical and C) 0 - 65% by weight of a (meth)acrylate of the formula II <IMAGE> wherein R' represents hydrogen or methyl and R2 represents an alkyl radical which is substituted by at least one hydroxyl group and has 2 to 6 carbon atoms, or represents a radical <IMAGE> wherein R3 and R4 denote hydrogen or methyl, R5 denotes hydrogen or a straight-chain or branched alkyl radical having 1 to 40 carbon atoms and n denotes an integer from 1 to 60, with the proviso that, when n represents 1, R5 simultaneously represents a straight-chain or branched alkyl radical having 1-40 carbon atoms.

Description

Field of the Invention

The invention relates to synthetic oils, the whole or partly from oligomers of or cooligomers of (Meth) acrylic esters and α-olefins exist.

State of the art

The often extreme requirements of what modern machines in terms of lubrication, have to develop synthetic lubricants (synthetic oils) performed. (See. Ullmann's Encyclopedia of Technical Chemistry, 4th edition, Vol. 20, 503-530, Verlag Chemie 1981). The common synthetic oils belong to various Substance classes on, in addition to polyethers, esters (from one and polybasic carboxylic acids with monobasic and polybasic Alcohols), phosphoric acid and phosphonic acid esters, Silicones, silicate esters, polyhalocarbons and fluorinated esters are polyolefins and Alkyl aromatics.

Polymers based on α-olefins of different provenances and with different polymerization process will. This is how polymers of α-olefins with 8-12 C atoms come in,  the z. B. using Ziegler catalysts or Catalysts obtained for ionic polymerization become important due to their good VI and Pour point values. Mixtures of such α-olefin oligomers with ester oils relatively good compatibility with rubber materials attributed to. Another benefit described is compared to the pure components better Miscibility of the olefin oligomers / ester mixtures with polar additives. Next are cooligomers or copolymers of α-olefins with (meth) acrylic acid esters as Mineral oil additives aroused the interest of technology. Compared to the more common pure ones Polymethacrylate polymer is enclosed by the α-olefin greatly increases the thermal stability of the additives improved.

Oil preparations are described in US Pat. No. 4,419,106 which is a hydrocarbon oil and a share in one Pour point depressant consisting of a copolymer approx. 10-90% by weight of alkyl acrylate units containing 8-20 Alkyl carbon atoms and 90-10 wt .-% α-monoolefin units with 12-40 C atoms per 100 wt .-% copolymer with one Have molecular weight Mw of 1000-100,000.

In US-A 39 68 148 and DE-A 22 43 064 z. B. Oligomers of this type are described, which consist of three Monomer groups are built up and their use as VI improver. Oligomers from:  

approx. 10-90% by weight of a 1-alkene with 4 to 32 C atoms
approx. 1-35% by weight of one or more alkyl (meth) acrylic acid esters with 8-34 C atoms in the alkyl radical and
approx. 1-35% by weight of one or more alkyl esters of (meth) acrylic acid or homologous, terminally unsaturated carboxylic acids with 1-4 C atoms in the alkyl radical.

The molecular weight of such oligomers is preferably _n = 1000 to 4000. The narrow molecular weight range achieved and the high uniformity of the products are emphasized. Furthermore, in US-A 40 09 195 an oligomerization process is described in which the most diverse (meth) acrylic acid derivatives, such as. B. C1-C4 alkyl esters in proportions of 1-35% by weight in addition to (meth) acrylic acid esters of C8-C34 alkanols in proportions of 1-45% by weight continuously and simultaneously to a mixture of radical initiators and 10 90% by weight of a 1-alkene having 4-32 C atoms are added in such a way that the essentially immediate molar ratio of acid derivatives to 1-alkene in the reaction mixture is kept relatively constant in the range from 0.001 to 0.2, the addition should take place at a temperature which does not impair the oligomerization.

From the same priority application as the aforementioned US-A is also the US-A 39 94 958 emerged in the Oligomer, the composition of which from the aforementioned US-A  is included, subsequently with an alkylenediamine Reaction was brought to dispersing VI improvers get. Furthermore, DE-A 32 23 694 describes copolymers of α, β-unsaturated Dicarboxylic acid esters with α-olefins claimed. The α, β-unsaturated dicarboxylic acid esters contain by definition as an alcohol component straight-chain or branched monoalcohols with 3-10 Carbon atoms; the α-olefins have 10-16 Carbon atoms. The copolymers can if necessary, be networked and your pour point should be are between -60 and 0 degrees C.

Copolymers containing isocyanate groups in the Molecular weight range 500-10,000 can by Solution polymerization of C1-C20 alkyl esters (Meth) acrylic acid and olefins with 1-alkenyl isocyanate are produced (see. DE-A 32 45 298). In the USA 45 26 950 becomes a manufacturing process for copolymers described, in which starting from at least one α-olefin with at least 6 carbon atoms and at least one unsaturated carboxylic acid or derivatives with the Olefins are copolymerizable in the presence of a Radical initiator the mixture of the components in Absence of solvents or diluents is heated to at least 135 degrees C, with none of the reactive monomers in excess is used to to avoid a thinning effect. Further in the SU-A 11 35 752 copolymers of decyl methacrylate and Tetradecene with a molecular weight of 8000-13 000 as Lubricating oil thickener claimed.  

EP-A 2 17 602 discloses oil additives based on ethylene copolymers, inter alia with ethylenically unsaturated mono- or dicarboxylic acids or their esters, which have a molecular weight _n of <1000.

Task and solution

The above-described prior art lets recognize that the class of methacrylate-α-olefin copolymers and their use as mineral oil additives a lot of attention has been paid. These So far, however, there was no connection class immediate technological connection with the so-called "synthetic oils". Prior art synthetic oils are usually from Hydrocarbons such as B. Oligomers of 1-decene and / or esters, for example dicarboxylic acid esters built up. (Ullmann's Encyclopedia of Technical Chemistry, 4th edition, vol. 20, 503-530, Verlag Chemie 1981).

However, both substance classes used have Disadvantage. The polyolefins show due to their non-polar Structure too low solubility when used with polar components, for example high pressure (EP) additives should be used. The esters have a polar structure As is known, serious disadvantages, such as. B. Problems with the miscibility with mineral oils, non-mineral oil-based Base oils as well as bad ones Sealing compatibility. In addition, the Give ester function for hydrolysis with the result  that the corrosion of metal parts is promoted. Attempts are made to overcome the disadvantages mentioned by mixing To compensate for hydrocarbons with esters in the Practice, however, requires considerable development effort assumes. Are the synthetic oil blends used Dispersing effectiveness for e.g. B. have black mud, it is necessary to add low or high molecular weight Add substances (e.g. "Ashless Dispersants" dated Polyisobutenyl succinimide type or VI improver with polar groups). This means a considerable amount Expenditure. In addition, these mostly contain nitrogen Connections can cause sealing problems. Provided the cooligomers CM used according to the invention Contain component C), dispersing effectiveness accomplished without the notorious problems at Use of, for example, nitrogenous monomers occur, especially seal intolerance.

It has now been found that the (meth) acrylic ester α-olefin cooligomers of the present invention Particularly meet the requirements of technology.

The present invention relates to synthetic oils containing in addition to the usual ingredients 5 to 100% by weight Cooligomer CM made up of:

• A) 0-75 wt .-%, preferably 10 to 70 wt .-%, whole especially 10-40% by weight of at least one 1-alkene 4 to 32 carbon atoms, preferably 10 to 14 Carbon atoms in the molecule  
• B) 20-100% by weight, preferably 40-90% by weight, of at least one (meth) acrylic acid ester of the formula I. wherein R represents hydrogen or methyl and R₁ represents an unbranched and / or branched alkyl radical or a cycloalkyl radical having 4 to 32 carbon atoms, preferably 8 to 20 carbon atoms in the alkyl radical
• C) 0-65% by weight, preferably 5 to 40% by weight, of a (meth) acrylic acid ester of the formula II wherein R 'represents hydrogen or methyl and R₂ for an alkyl radical having 2 to 6 carbon atoms substituted by at least one hydroxyl group or for a radical wherein R₃ and R₄ are hydrogen or methyl, R₅ is hydrogen or an optionally branched alkyl radical having 1 to 40, preferably 1 to 20 carbon atoms and n is an integer from 1 to 60, with the proviso that when n is 1, R₅ simultaneously stands exclusively for an optionally branched alkyl radical having 1 to 40 carbon atoms.

The components A), B) and C) in the cooligomers CM should complement each other 100%. The cooligomers according to the invention are in the Molecular weight range Mw 1000 to 100,000, preferably 1,500 to 25,000 (determined by Gel permeation chromatography, cf. H.F. Mark et al. Encyclopedia of Polymer Science & Technology Vol. 10, 1-19, J. Wiley 1987).

Examples of representatives of component A) include:
Butene-1, Penten-1, Hexen-1, Hepten-1, Octen-1, Nonen-1, Decen-1, Undecen-1, Dodecen-1, Tridecen-1, Tetradecen-1, Pentadecen-1, Hexadecen- 1, Heptadecen-1, Octadecen-1, Nonadecen-1, Eicosen-1, Heneicosen-1, Docosen-1, Trocosen-1, Tetracosen-1, Pentacosen-1, Hexacosen-1, Heptacosen-1, Octacosen-1, Nonacosen-1, Triaconten-1, Hentriaconten-1, Dotriaconten-1, or the like. Also suitable are branched-chain alkenes, such as, for example, vinylcyclohexane, 3,3-dimethylbutene-1, 3-methylbutene-1, diisobutylene-4-methylpentene-1 or the like.

Alkenes-1 with 10 to 32 are also suitable Carbon atoms involved in the polymerization of ethylene, Propylene or mixtures thereof are obtained, these Materials in turn made from hydrocracked materials be won. The embodiment in which the Component A) of the cooligomers CM for 1-decene, dodecene or stands for tetradecene. Is very particularly preferred Decen, the best in its use Low temperature behavior (pour point) is registered.  

Also of particular interest are cooligomers CM in which component B) consists of (meth) acrylic esters with 4-24, preferably 8-22 carbon atoms in the alkyl radical or mixtures thereof. May be mentioned for. B. the monomers:
Butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, Isodecylarylat, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, Dodecylpentadecylacrylat, hexadecyl, Heptadecylacrylat, octadecyl acrylate, Cetylstearylacrylat, oleyl, Nonadecylacrylat, eicosyl acrylate, Cetyleisosylacrylat, Stearyleisosylacrylat, Docosyl acrylate, or the corresponding methacrylates Eicosyltetratriacontylacrylat .

Highlighted its alkyl methacrylate with C10 im Alkyl radical with a higher proportion of iso. Mentioned his z. B. C12-C15-alkyl ester of methacrylic acid with approx. 60-90% Iso content and isodecyl methacrylate, with a high Degree of branching favorable to the low-temperature behavior, including the pour point and a certain C number distribution the viscosity-temperature behavior improved.

Cooligomer CM are of the type described State-of-the-art synthetic oil components comparable in terms of characteristics such as viscosities, VI index, Low temperature behavior, evaporation and Oxidation stability and other practical ones Properties. Compared to the described prior art, they point but the following advantages: Due to the combination of polar monomers with non-polar there are no miscibility problems with  Mineral oils, poly-α-olefins (PAO), esters or others Basic liquids and no solubility problems with additives. The sealing behavior is absolutely neutral. Corrosion due to acid formation can also occur be excluded. In addition, it was surprisingly found that Synthetic oil mixtures of the cooligomers CM z. B. with Polyolefins and / or esters clearly compared to the Individual components have increased VI index, which indicates the Influence of the oligomer is due. Farther causes the cooligomer component CM that clearly lower low-temperature viscosities than e.g. B. with synthetic hydrocarbons are possible. (Measured in the Cold Cranking Simulator, see Example 12). The Behavior when there is a strong thermal-oxidative load despite partially existing double bonds excellent (Example 18, VW TD engine test, comparison with PAO formulation). Are oligomers used as a synthetic oil component, the also contain component C) in a sufficient amount, so good dispersing effect is given, due to the oxygen-containing dispersing group Seal problems are avoided and there is no loss in the shear stability of the mixture, as z. B. when using high molecular VI improvers occur.

All of this has the consequence that the characteristics for the different mineral oil specifications without or with one lower proportion of high molecular VI improvers are reachable. This results in u. a. Advantages at the shear stability. The risk of Formation of deposits.  

The synthetic oils

Among "synthetic oils" are particularly those of Technology preferred polyalphaolefins (PAO) as well as the organic esters (OE) such as dicarboxylic acid and polyol esters understood (see E. I. Williamson, J. Synth. Lubr. 2 (4) 329-341 (1986); 3 (1) 45-53 (1987); A. Plagge, Tribology and Lubrication Technology 34, 148-156 (1987); Ullmann, 4th Edition, vol. 20, loc.cit. Pp. 514-821). Serve as starting materials for the polyalphaolefins primarily crack olefins, predominantly with a boiling point between 30 and 300 degrees C. The polyalphaolefins correspond in the Rule of the general formula III

wherein R is an alkyl radical, in particular 6-10 Carbon atoms stands with a molecular weight of usually 300-6000 (w).

The organic esters (OE) are, on the one hand, the esters of Dicarboxylic acids with 3 to 17 carbon atoms such as adipic acid, Azelaic acid and sebacic acid with primary alcohols mentioned - as the most important alcohol component in this Case to apply polyalkylene glycols - on the other hand, the Monocarboxylic acid esters, especially the esters of C6-C12 carboxylic acids with in particular branched alcohols, especially those with the neopentyl framework like  Neopentyl alcohol, trimethylolpropane and pentaerythritol. The ester oils have a high adsorption capacity Metal surfaces and therefore good lubricity, but at the price of relative sensitivity against (hydrolytic) degradation, so that corrosive Degradation products can occur. The viscosities range e.g. B. values around 5.9 [mm² / s 38 degrees C] for the neopentyl glycol ester of n-C7 acid to to 16.2 for the corresponding ester of n-C12 acid, or of value 12.1 for the trimethylolpropane ester of n-C6 acid up to 36.4 for the corresponding ester of n-C12 acid.

Production of the cooligomers CM

As is known from the prior art, the Cooligomers of the type claimed under certain Prerequisites through radical-induced polymerization produce, for example by thermal polymerization and with the addition of a suitable initiator or Redox systems. The polymerization can take place in the absence of a Solvent but also in the presence of suitable Solvents are carried out. So everyone can conventionally designated as polymerization media Solvents are used, as well as mineral oils, HC oils, PAO, ester or already made oligomer. Here can e.g. B. the 1-alkene according to component A) in one suitable reaction vessel specified and on a suitable reaction temperature are brought. in the generally a temperature range from 80 to  200 degrees C, especially 160 ± 20 degrees C as more appropriate Area apply. One gives in the same Temperature range, preferably in the feed over a certain period, for example 0.25-10 hours, for example within 5 1/2 hours component B) or B) + C) in the proportions intended for this. It is advisable to leave some time, usually some Hours - about 6 hours should be mentioned - in Polymerize batch. It has proven to be advantageous proved to be the initiator throughout the reaction add z. B. in portions in about thirty minutes Intervals or continuously in the manner of a Inlet procedure. Well-known initiators come Radical starters in question (see Kirk-Othmer, 3rd Ed., Vol. 13, pg. 355-373, Wiley Interscience 1981; Rauch puntigam loc.cit). The total amount of initiator used are generally in the range 0.1-10% by weight, preferred in the range 0.1-5 wt .-% based on the total of Monomers. It is advisable to choose initiators whose Decay characteristics of the polymerization modalities are adjusted. As a guideline, a half-life of Initiator (in Bezol) at the reaction temperature of called about 0.25 hours. These include e.g. B. peroxidic initiators such as di-tert-butyl peroxide. As an indication, the addition of 0.001-0.005 mol Initiator per portion given in portions. According to the available results, an extensive one occurs Reaction of the monomers, for example by 98%, so that separation of the monomers in many cases, yes even further processing is unnecessary. Are the Requirements e.g. B. up to the flash point, it must Residual monomers are removed.  

The products i. a. colorless, oily liquids that is completely mixed with mineral oil, PAO, HC oils and Mix ester oils.

The following examples serve to illustrate the invention:
The physical data are determined using the following standards: (See Ullmann 4th edition vol. 20 loc.cit, FH Mark et al. Vol. 10. loc.cit).

Viscosity: η (100 degrees C and 40 degrees C) (according to DIN 51 562 or ASTM D 445 in the Ubbelohde capillary viscometer)
VIB calculates from the 40 and 100 degree viscosity of the base oil
Pour point: in the pour point machine according to DIN 51 583,
Molecular weight: (by gel chromatography against PMMA as standard)
Br number: according to DIN 51 774
Noack number: according to DIN 51 581; inconsistency: U = -1 (according to GPC)

The abbreviation "AMA" used in the following stands for Alkyl methacrylate, "PAO" stands for polyalphaolefin, "TMA-OD-Ester" stands for the ester of trimethylolpropane with adipic acid.  

Examples Production of synthetic oil components example 1

1 mol of 1-decene (140 g) is in the reaction vessel Heated 160 degrees C. A mixture of 0.5 mol Isodecyl methacrylate (113 g) and 0.5 mol C12-C15 alkyl methacrylate with 60% iso content (136 g) let run for 4 hours. At the end of the inflow is polymerized in batch for a further 12 hours. While the total response time from here is 16 hours Exception of the last hour at 30 minute intervals di-tert-butyl peroxide added as initiator (here 30 Servings, total amount 2.8% by weight based on the Monomers). At the end of the reaction, the conversion of the monomers is included about 98%. The product is a colorless, oily liquid that complete with mineral oils, poly-olefins or ester oils is miscible.

Substance data:
η (100 degrees C) = 45.1 mm² / s,
η (40 degrees C) = 489.0 mm² / s
VIB = 146
Pour point = -43.2 degrees C.
w = 4000
n = 1790 U = 1.23
Evaporation loss according to Noack = 4-5% by weight

Example 2

Carried out as in Example 1, but inflow of Methacrylate mixture for 1.5 hours.

Substance data:
η (100 degrees C) = 94.9 mm² / s,
η (40 degrees C) = 1210.8 mm² / s,
VIB = 164
Pour point = -33.6 degrees C.
w = 8330
n = 2280
U = 2.65
Monomer conversion = 95%

Example 3

Like example 1, but reaction temperature but 140 degrees C, initiator used: tert-butyl perbenzoate

Substance data:
η (100 degrees C) = 87.8 mm² / s
η (40 degrees C) = 1188.3 mm² / s
VIB = 154
Pour point = -34.7 degrees C.
w = 6890
n = 2240
U = 2.00
Monomer conversion = 97%.

Example 4

2 mol of 1-decene (280 g) are in the reaction vessel Heated 160 degrees C. 1 mol of isodecyl methacrylate (227 g) allowed to run for 5 hours at this temperature. After the end of the feed there will be another 6 hours in batch post-polymerized. During the entire response time of 11 hours will be 30 minutes with the exception of the last hour Distances di-tert-butyl peroxide as an initiator added (here 20 servings total 4.3% by weight based on the monomers). At the end of the reaction, the conversion of the monomers is included about 92%.

Substance data:
η (100 degrees C) = 25.9 mm² / s
η (40 degrees C) = 250.3 mm² / s
VIB = 134
Pour point = -48.4 degrees C.
w = 2240
n = 1370
U = 0.64

Example 5

As example 4, but isodecyl methacrylate / decene 1: 1 mol, Total amount of initiator 2.8% by weight.

Substance data:
η (100 degrees C) = 47.6 mm² / s
η (40 degrees C) = 603.8 mm² / s
VIB = 132
Pour point = -38.9 degrees C.
w = 3120
n = 1610
U = 0.94

Example 6

As example 4, but isodecyl methacrylate / decene in Ratio 1: 0.25 mol ratio, total amount of initiator = 2.8% by weight

Substance data:
η (100 degrees C) = 424.6 mm² / s
η (40 degrees C) = 1219.7 mm² / s
VIB = 170
Pour point = -10.7 degrees C.
w = 12,300
n = 2890
U = 3.26
Monomer conversion = 98%

Example 7

As example 6, but feed of the isodecyl methacrylate during 2.5 hours, total amount of initiator = 2.8% by weight

Substance data:
η (100 degrees C) = 888.2 mm² / s
η (40 degrees C) = 27 162 mm² / s
VIB = 206
Pour point: (too viscous)
w = 24,800
n = 3480
U = 6.12
Monomer conversion <99%

Example 8

As example 5, but reaction temperature 140 degrees C, Initiator: tert-butyl perbenzoate 4.8% by weight.

Substance data:
η = (100 degrees C) = 130.7 mm² / s
η = (40 degrees C) = 2335.1 mm² / s
VIB = 147
Pour point = -25.9 degrees C.
w = 6690
n = 2200
U = 2.04
Monomer conversion = 96%

Example 9

As example 5, but reaction temperature 126 degrees C, Initiator: tert-butyl personoate 4.8% by weight.

Substance data:
η (100 degrees C) = 460.1 mm² / s
η (40 degrees C) = 12,321.7 mm² / s
VIB = 180
Pour point = -8.5 degrees C.
w = 11,800
n = 2560
U = 2.31
Monomer conversion = 88%

Example 10

Procedure as in Example 4, but in addition to 1 mol of 1-decene 280 g in the template according to Example 4 prepared synthetic oil used as a solvent.

Substance data:
η (100 degrees C) = 28.0 mm² / s
η (40 degrees C) = 294.0 mm² / s
VIB = 127
Pour point = -44.5 degrees C.
w = 2180
n = 1350
U = 0.61
Monomer conversion = 98%

Example 11

Like example 1, but methacrylate component Butyl methacrylate, feed time 3.5 hours.  

Substance data:
η (100 degrees C) = 148.0 mm² / s
η (40 degrees C) = 2836.2 mm² / s
VIB = 147
Pour point: -26.3 degrees C.
w = 6500
n = 1860
U = 2.51
Monomer conversion = 91%

Example 12

3 mol of dodecane (523 g) are in the reaction vessel Heated 160 degrees C, with 1 mol of C12-C15 alkyl methacrylate 90% iso content (272 g) is circulated for 5.5 hours calmly. After the end of the inflow, another 11 hours in Batch post-polymerized. The initiator is added as described in Example 1. After the reaction, it will Removed solvent by distillation. The product obtained is a colorless, oily liquid that is completely compatible with Mineral oils, PAO or ester oils are miscible.

Substance data:
η (100 degrees C) = 16.7 mm² / s,
η (40 degrees C) = 128.1 mm² / s
VIB = 141
Pour point <-52.1 degrees C.
w = 1510
n = 1230
U = 0.23
Evaporation loss according to Noack 6%
Monomer conversion = 95%

Example 13

Like example 12, but the same instead of dodecane Weight amount of hydrocrack oil as a solvent.

Substance data for hydrocrack oil:
η (100 degrees C) = 3.62 mm² / s
VIB = 126
Pour point = -33.0 degrees C.

Material data of the oligomer / oil mixture obtained:
η (100 degrees C) = 5.08 mm² / s
η (40 degrees C) = 24.1 mm² / s
VIB = 144
Pour point = -34.5 degrees C.

Example 14

400 g (0.28 mol) C1 (C1 is the methacrylic acid ester of an ethoxylated C16-C18 fatty alcohol mixture, middle Degree of ethoxylation 25, here the alcohol is Marlipal 1618 / 25®, product from Hüls AG.) Are used in 450 g (1.99 mol) Isodecyl methacrylate dissolved. 250 g (1.78 mol) 1-decene are heated to 140 degrees C in the reaction vessel. While The methacrylate mixture will run in for 1.5 hours calmly. After the end of the feed, another 15 hours in Batch post-polymerized. The initiator is added as described in Example 1. The initiator is tert-butyl perbenzoate, Total amount ≈3% by weight. The received Product is a yellowish oil that is soluble in mineral oil.  

Substance data:
η (100 degrees C) = 1006 mm² / s
η (40 degrees C) = 15 756 mm² / s
VIB = 276
Pour point: (too viscous)
w, n = cannot be determined via GPC due to strong adsorption.
Yield <98%

Example 15

300 g (0.37 mol) of component C2 (C2 is the methacrylic acid ester of Methoxypolyethylene glycol medium degree of ethoxylation ≈16; here the alcohol Carbowax 750® (Trademark Union Carbide) is used in 400 g (1.77 mol) Isodecyl methacrylate dissolved. 300 g (2.14 mol) of 1-decene heated to 160 degrees C in the reaction vessel. The Methacrylate mixture will run in for 2 hours calmly. Total reaction time 16.5 hours, initiator addition as in Example 1. Initiator: di-tert-butyl peroxide, total amount 3% by weight. The product is Soluble in mineral oil.

Substance data:
η (100 degrees C) = 293.4 mm² / s
η (40 degrees C) = 3999.0 mm² / s
VIB = 217
Pour point = -22.1 degrees C.
w, n cannot be determined via GPC due to strong adsorption
Sales almost 100%

Example 16

As example 5, but instead of isodecyl methacrylate C12-C15 alkyl methacrylate with 90% iso content

Substance data:
η (100 degrees C) = 41.8 mm² / s
η (40 degrees C) = 417.6 mm² / s
VIB 152
Pour point = -44.1 degrees C.
w = 3430
n = 1830
U = 0.78

Example 17

As example 1, methacrylate component but C12-C15 alkyl methacrylate 90% iso), AMA / decene ratio: 1: 0.5 mol, 1 hour AMA feed.

Substance data:
η (100 degrees C) = 234.4 mm² / s
η (40 degrees C) = 4810.6 mm² / s
VIB = 165
Pour point = -25.6 degrees C.
w = 23 100
n = 3230
U = 6.14

Application engineering examples Example 18

Comparison of an oligomer / ester oil mixture with a poly-α-olefin / ester oil mixture in the viscosity data

It is clearly recognizable that with the cooligomer in the Mixture despite higher viscosity at 100 degrees C. lower viscosity at -30 degrees C and thus a better low-temperature behavior can be achieved.

Example 19

Comparison of an oligomer / PAO formulation with a PAO 6 / PAO 40 formulation in the VW TD engine test

So with the oligomer / PAO mixture is an excellent one To achieve diesel rating, what very good thermal-oxidative Stability speaks. To be considered furthermore that the pure PAO formulation used as a comparison known to have very good diesel performance having.

Claims (1)

Synthetic oils containing 5 to 100% by weight of cooligomers of (meth) acrylic acid esters and 1-alkenes in addition to constituents which are customary per se, characterized in that the cooligomers CM are composed of

• A) 0-75 wt .-%, at least one 1-alkene with 4 to 32 carbon atoms in the molecule
• B) 20-100% by weight of at least one (meth) acrylic acid ester of the formula I. wherein R represents hydrogen or methyl and R₁ represents an optionally branched alkyl radical or a cycloalkyl radical having 4 to 32 carbon atoms in the alkyl radical
• C) 0-65% by weight of a (meth) acrylic ester of the formula II wherein R 'represents hydrogen or methyl and R₂ for an alkyl radical having 2 to 6 carbon atoms substituted by at least one hydroxyl group or for a radical wherein R₃ and R₄ are hydrogen or methyl, R₅ is hydrogen or an optionally branched alkyl radical having 1 to 40 carbon atoms and n is an integer from 1 to 60, with the proviso that when n is 1, R₅ simultaneously represents an optionally branched alkyl radical 1-40 carbon atoms.