DE1745359A1 - Process for the production of lubricating oil additives - Google Patents

Description

RÖHM & HAAS

DÄRMSTADT

Pat "Dr, Hh / RS / 10

Process for the production of Sehmier oil additives

Lubricating oil additives with dispersing and detergent effects are already known which consist of addition products of certain polyamines with polyisobutylene. Such graft copolymers are Z ₄ B ₈ according to US Patent 3,087,875 by radiation-chemical polymerization of nitrogen-containing monomers in the presence of polymers of higher methacrylic acid esters.

On the other hand, lubricating oil additives according to German patent specification 1,118,971 are produced on an industrial scale by polymerizing monomers containing oil-soluble * borrowed polymers by free radicals to 40 to 85 % and then adding a nitrogen-containing monomer, whereupon the polymerization is continued until conversion is complete * A satisfactory one Dis "pergierwirkung, the products so prepared, when they have a content of, for example, B" is at least 8 weight "" ^ N-vinyl-pyrrolo "lidon in the polymer contain.

Products of improved effectiveness are obtained according to the main patent "**""_#" (R jj8 086 IVd / 39 c), if one is in the presence of a base polymer, the

103836/1147

- Ρε) from acrylic or methaerylic acid esters rait at least 8, preferably 12 to 16 carbon atoms in the alcohol radical or fuiaar or itaconic acid esters with 8 to 18 carbon atoms in the alcohol residue or off Mixtures of these esters with one another or with smaller amounts of aryl or methaeryl esters with 1 to 4 carbon atoms in the alcohol radical, aminoalkyl esters acrylic or methacrylic acid, vinyl acetate or mixtures of these monomers,

b) from isobutylene

is constructed polymerizing an unsaturated compound having a tertiary nitrogen atom rauLkalläuti, wherein the proportion of the unsaturated compound of 2 to 30 ßew * ~ $ _# based on the Basispolymerlsat ,, constituted The preferred amount range is from 3 to 4.5 Gaw "~ # · As nitrogen-containing compound is warping, N-vinyl »pyrrolidone used" under "radikaliseher polymerization" is in this case the. * such as azo compounds or peroxides, triggered, not triggered by high-energy radiation polymerization verstandest additions of about 3% of such graft copolymers impart Sehmierölen by radical-forming polymerization initiators good dispersing properties, but leave only 75 points in the MWM diesel test run over 50 hours according to that of E, Kruppke ("The Engine Testing of Crankcase Lubricating Oils" 1962, pages 53 - 67, "Engine Testing and Evaluation of Crankcase Lubricants") Achieve the assessment method established for the detergent effect.

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■ 17A5359L

An increase in effectiveness beyond this value is only by significantly increasing the proportion of nitrogenous Monosnereii possible

It has now been found * that the detergent effect of the products according to the Haus> ptpatent can be increased considerably if as nitrogen-containing unsaturated compound polymerizable derivatives of Iraidasol of the general formula

R NO

J.

- R

wherein R is a group with a polymerizable carbon double bond, such as the vinyl «, Isopropenyl, aaryloxyalkyl or methaeryloxyalkyl group,

and H * same or different radicals from

Group are hydrogen, alkyl and aralkyl and two radicals R ¹ on adjacent carbon atoms can be closed to form a ring,

be used "These monomers are used in amounts up to 30 percent by _e - applied $, vorisiigsiieise 2 to 10 percent '' ^, but in addition to a minimum content of 2%, other nitrogen-containing monomers mentioned in the main patent can also be used, for" B * N -Vinyi-pyrrolidone, N-vinylsuccinimide, N-vinyl-N-ethylacetamide or ii-tinyl-H-ynethylbenzamide

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m 4 ~

a) Acrylic or methacrylic acid ester !! with at least 8, preferably 12 to 1β, carbon atoms in the alcohol residue or fumaric or itaconic acid esters with 8 to ^ 18 carbon atoms in the alcohol residue or from mixtures of these esters * optionally in minor amounts from acrylic or methacrylic esters with 1 to 4 carbon atoms in the alcohol radical Aminoalkyl esters of acrylic or methacrylic acid, Vinyl acetate or mixtures of these monomers,

b) from isobutylene

and their grafts are at least partially made up of one of the imidazole derivatives described in more detail above and ^H for the remainder -f optionallyV of one or more unsaturated compounds with a tertiary nitrogen atom * where the weight of the grafts is 2 - J50 %, based on the weight of the main chain »

In addition to units of nitrogen-containing monomers, the graft branches also units of nitrogen-free esters of acrylic, methacrylic, Itaconic or fumaric acid contain "Such 'graft copolymers are formed, for example," when the production of the Base polymer used ester mixture has not been completely polymerized, so that the unpolymerized part is polymerized by grafting together with the nitrogenous monomers »

The superior detergent effectiveness of imidazole derivatives in Graft copolymers were surprising and not predictable, since similarly constructed nitrogen compounds, e.g. vinylpyrrolidone, do not achieve a similar detergent effect at least as long let, like the proportion of these nitrogen compounds, not multiply the amount to be used according to the invention polymerizable imidazole derivatives is increased «

The special effect of the polymerizable imidazole derivatives is already demonstrated in the descendants of the basic body, e.g. «B» the N-vinylimidazole, clearly, but occurs particularly in the case of the 2-digit ~ alkyl-substituted imidazole derivatives in evidence * Among these is the descendants of 2-methyl,

109836 / 1U7 - 5 -

- 5'- ■

Special mention should be made of 2-ethyl, 2-isopropyl and 2-t-butyl imidazoles, "Due to their good technical accessibility, those imidazole derivatives are preferred which have an N-vinyl group as a polymerizable group." Other suitable groups are, _e B "the N-Methacryloxyäthyl- or the N-Acrylamidoäthylgruppey With simultaneous assessment of the technically ready availability of good polymerizability and the induction of high dispersing and detergent effect are the l-vinyl-2-methyl-imidazole and l ~ Particular emphasis should be placed on vinyl-2 «" a ethyl-imidazole *

The polymerization is usually carried out as a solution polymerization in oil with one of the known radical-forming initiators, such as azodiisobutyric acid dinitrile, azodiisobutyric acid diethyl ester, tert-butyl perbenzoate or tert-butyl perbenzoate, advantageously with the exclusion of air. The polymerization is carried out in other solvents at least possible"

A lubricating oil that, with about 6 % of a lubricating oil additive,? which has been in the context of the invention 4.5% t relative prepared 2-imidazol-'methyl' on the base polymer, l-vinyl ~ \ is added, can be in the MWM diesel test run for 50 hours to reach 92 points, while an equivalent result can only be achieved with an equal heights addition of a graft polymer of N-Vinylpyrröl-idons when more than J50% of this monomer used for the production of the graft polymer * using 15% vinylpyrrolidone you against it as only reached 85 points "

The molecular weight of the graft copolymers is essentially determined by that of the base polymer used *

1 0 9 8 3 ^{6/1 1 A 7 ßAE3}

The molecular weight of the end product is increased compared to that the base polymer through the graft polymerization depending on the amount of the grafting monomer * For lubricating oil additives, in the previously usual proportions in iSchmier « oils are to be used, one generally assumes Base polymers with molecular weights from 400,000 to 1 million from * It is preferred, however, to use base polymers to use with molecular weights below 150,000 and for this fc the lubricating oils correspondingly larger amounts of the obtained Adding graft polymer »The service life of the alloyed lubricating oils is thereby considerably increased * without it the undesired piston deposits comes to the expert as a consequence of the addition of polymers as lubricating oil additives are known * These properties of the invention manufactured products makes the use of additional Detergents dispensable »

It has also been found that such products produced by the process of the invention, for which a base polymer with molecular weights of 10,000 to? The process of the invention is therefore carried out with particular advantage with such base polymers. The economic disadvantage is that relatively large amounts of these particularly low molecular weight graft polymers, namely about 10 to 12 %, have to be added to the lubricating oil , on the other hand, there is the advantage that the total amount of additives required is not, or not substantially, the amount range customary hitherto due to the saving of an additional detergent

- Ύ mm

10 9 8 3 8/1147 BAD ORIGINAL

exceeds «, base polymers have molecular weights below 5ΟΌΟ are for making lubricating oil additives that ! Invention no longer suitable.

The lubricating oil additives according to the invention can be added to any commercially available base oil. relatively large amounts of a low molecular weight graft polymer used together with a low viscosity base oil "Such combinations can be considered real multi-range" - oils are designated * ^

The preparation of the mixed graft polymers of the invention is described in the following examples. The molecular weights of base polymers designated Mw are Ge "- weight averages _a you solution of butyl acetate at 20 ° C with the photo-Gonio-Dlffusometer the company Sofica measured by the light scattering method in" The implementation and evaluation of the measurement, the device may have been accompanying Instructions followed exactly *

The lubricant and detergent action of the graft copolymers obtained was determined according to the method described by E. Kruppke {"! Ehe Engine Testing and Evaluation of Crankcase Lubricants" in "The. ™ Engine testing of Crankcase Lubricating Oil"_# 1962 ^ page _55-67? a «s" Report of the Institute of Petroleum Conference "Brighton ^ 1?» - I9.56l) described MWM Biesel test run over 50 hours assessed · The basis of assessment is the construction of the Kolbense. Complete cleanliness is rated with 100 points, total pollution with 0 points «,

- ■ 8 -

10SS36 / 1147

Example 1; '*

* 90 wt -Teiles of a copolymer (having a Mw of approx * 70 000 determined by light scattering) of 10 Gews "parts by methyl methacrylate and 90 parts by weight of a mixture of _e methacrylic acid esters of fatty alcohols (average number of carbon atoms 14 * 0)> dissolved in 100 parts by weight of mineral oil (viscosity of the mineral oil bei.98,89 ° C = 4.0 cSt) are mixed with 10 parts by weight _o l-vinyl-S-methyllraidaZol and 0.5 wt "portions tert (50-JoIg in mineral oil) Butylperbenzoatlösung and with stirring and exclusion of air ca "8 hours at IJO C polymerized" After a reaction time of 1 and 3 hours, respectively 0.1 _e · "parts of tert» - * butyl yielded benzoatlösung! and polymerized "

The MWM diesel test run results in 9I points according to the one described above Investigation method »

Example 2?

95 parts by weight of a copolymer (Mw approx »^ O 000)

4 wt # * thy "parts Me! Acrylate 10 weight" parts by methyl methacrylate and 86 Gewfr parts of a mixture of methacrylic acid esters of fatty alcohols (average number of carbon atoms l4 _t 0) * dissolved in 100 wt, parts by the mentioned in Example 1, mineral oil * are with

5 parts by weight of vinyl vinyl 2-ffiethylimidazole and 0.5 parts by weight tert »-Butyl perbenzoate solution (50- ^ ig / in mineral oil) added and with stirring and closed air for about 8 hours at 150 ° C polymerized *

The piston cleanliness after the MWM diesel test run is with 90 points rated *

- 9 w

109836/1147

Example 3: i

The procedure according to Example 1 is with the difference repeats that instead of l-vinyl-2-methylimidazole l ~ vinyl-2-ethylimidazole is used »

With the resulting graft copolymer can be im MWM diesel test ran a piston rating of 89 points achieve*

Example 4s .

90 parts by weight of a copolymer (MW approx. 70,000) composed of 45 parts by weight of butyl methacrylate and 55 parts by weight of a mixture of methaerylic acid esters of fatty alcohols (average carbon number 1.4.0), dissolved in 100 Parts by weight of mineral oil * are mixed with 10 parts by weight of 1-vinyl "2-raethylimidazo! and 0.5 parts by weight of tert "-Bütylperbenzoatlösung (50 ^ in mineral oil) was added and polymerized with stirring and exclusion of air for about 8 hours at ⁰ I30 C * After a reaction time of 1 * · and 3 hours are each 0, 1 wt _e parts by the tert "-Bütylperbenzoatlösung relented and of poly" merized "After the MWM Dieselprüflauf the piston cleanliness is rated 90 ^ points.

Example 5 ^L i

Example 1 is repeated with the difference that instead of 1-vinyl-2-methylimidazole das! «- vinylimidazole is used,

In the MWM »Diesel test 86 points are achieved«

m 10 -

109836/1147

1/45359

Example 6:

Following the procedure of Example 1 is a graft polymer produced with a base polymer of Mw 500,000 «

The MWM test run results in 88 points «

Verification test %

85 parts by weight of a copolymer (Mw approx. JO 000) from 10 parts by weight of methyl methaorylate and 90 parts by weight of a mixture of methacrylic acid esters of fatty alcohols (average carbon number 1 ^, 0) dissolved in 100 parts by weight Parts of mineral oil, 15 parts by weight of N-vinyl-pyrrolidone and 0.5 parts by weight of tert-butyl perbenzoate solution are added and the mixture is polymerized for about 8 hours at 50 ° C while stirring and with the exclusion of air.

After a reaction time of 1 and 5 hours, respectively 0.1 parts by weight of the tert-butyl perbenzoate solution were added and fully polymerized »

In the MWM diesel test run, 85 points are achieved.

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109836/1147

Claims (1)

θ. m. fe, ». CHEMICAL FABITIiC claims; It,) graft copolymers, the main chain of which consists of a) acrylic or methacrylic acid esters with at least 8, preferably 12 to 1.6 carbon atoms in the alcohol residue or pumaric or itaconic acid esters with 8 to 18 carbon atoms in the alcohol residue or from mixtures of these esters with one another or with lower ones Amounts of acrylic or methacrylic esters with 1 to 4 carbon atoms. μ in the alcohol residue, arainoalkyl esters of acrylic or methacrylic acid, vinyl acetate or mixtures of these monomers,. or b) are made up of isobutylene and their graft branches are made up of unsaturated compounds with a tertiary nitrogen atom, the weight of the graft branches being 2 to 50% by weight, based on the weight of the main chain, according to the main patent * · »» · » , (R J8 086 IVd / 59 c), characterized in that the nitrogen compounds building up the graft branches are at least partially made up of a polymeric derivative of imidium oil with the general formula Rl in which R is a group with a polyraerizable carbon double foil, such as vinyl, isopropenyl -, Acrylöxyalkyl- or methacrylöxyalkyl group, 1.0983.6 / 1147 and R ^{f are} identical or different radicals from the group consisting of hydrogen, alkyl or aralkyl and two adjacent radicals R ^! to / ^ .-- y \ can be closed in a ring, and / for the rest of / ^ if necessary ^ from one or more other unsaturated compounds with a tertiary nitrogen atom '! " 2) Graft copolymers according to Claim 1, characterized in that that the graft branches are at least partially built up from such a polymerizable derivative of imidazole, which is alkylated in the 2-position. 5 ·) Graft copolymers according to Claims 1 and 2, characterized characterized in that the graft branches are at least partially composed of l-vinyl-2-methyl and / or l-vinyl-2-ethyl-imidazole are. 4,) graft copolymers according to claims 1 to 3, characterized characterized in that the molecular weight of the main chain is between 5000 and 150,000, 5 ») Graft copolymers according to claims 1 to 4, characterized in that the molecular weight of the main chain is between 10,000 and JO, 000« 6,) Process for the production of lubricating oil additives, in which in the presence of a base polymer, the a) from acrylic «or methacrylic acid esters with at least 8, preferably 12 to 16 carbon atoms in the alcohol residue or pumaric or itaconic acid 109836/1 U7 esters with 8 to 18 carbon atoms in the alcohol residue or from mixtures of these esters with one another or with smaller amounts of acrylic or methacrylic esters with 1 to 4 carbon atoms in the alcohol radical, aminoalkyl esters of aoryl "» or methacrylic acid, Vinyl acetate or mixtures of these monomers, or b) from isobutylene is built up, an unsaturated compound with a tertiary nitrogen atom is radikalisoh polymerized, The proportion of these compounds, based on the base polymer used, is 2 to 30% by weight »*] characterized in that the unsaturated nitrogen compound a polymerizable derivative of imidazole with the general formula wherein R is a group with a polymerizable ä carbon double bond, such as the vinyl, isopropenyl, acryloxyalkyl or methaoryloxyalkyl group, and R ^{1 are} identical or different radicals from Group is hydrogen, alkyl or aralkyl and two adjacent radicals R ¹ can be closed to form a ring; is used, . x) according to the main patent. ,., w .- (R 38 086 IVd / 39 o) - 14 - 109836/1147 7 ·) Process according to claim 6, characterized in that the polymerizable derivative of the imidazole is a 2-alkyl-substituted one Imidazole derivative is used. 8t) Process according to claims 6 and J, characterized in that the polymerizable derivative of the imidazole of the l-vinyl «2-methyl- and / or the l-vinyl-2-ethyl« imidazole is used « 9) Process according to Claims 6 to 8, characterized in that that a base polymer with a molecular weight between 5000 and 150,000 is used. 10 ») Process according to claims 6 to 9», characterized in that a base polymer with a molecular weight of 10,000 to 70,000 is used. 11,) graft copolymers according to claims 1 to 5 * characterized in that the graft branches in addition to 2 to "30 Gew» «# based on the weight of the main chain, Ein units of nitrogen-containing monomers additional units of nitrogen-free esters of acrylic, methacrylic, Contain itaconic or fumaric acid " 12.) Process according to claims 6 to 10, characterized in that that the polymerization of the unsaturated nitrogen compound in the presence of a base polymer and additionally carried out by monomeric nitrogen-free esters of acrylic, methacrylic, itaconic or fumaric acid will, 1 0 98 36/1 U .7