DE1444884C - Oil mixtures - Google Patents

Description

C _n H _2n N NH '■ m, possible. This creates an amide bond from the pri-

V / · \ 55 mary nitrogen to the carboxy group of the anhydride building- '"- ■ . ·.''■ £ ■ - -.- ■. ■■ · steins. ■.; ■ ■■ · .. ■:';; - \ J \. \. [;., ■. ■ .. '■.. ■ , / ... · ■.

Il The other carboxy group is generally to

O a carboxyl group. If the aminoalkyl compound

is used in excess, this acid group

i 60 go into salt form. Will the reaction mixture

carries, in which A further heats an alkylene group with 2 or 3 carbon atoms, then some or all of the

represents lenstoffatomen and η a value of 2 or 3 last-mentioned groups of imide groups. *

possesses, and where the proportion of the maleamine or the oil-soluble graft copolymers with the

Itaconamic acid groups about 1 to 22, preferably grafted building blocks from dibasic ole-

up to 11, percent by weight of the graft copolymeric acid anhydrides are mixed with aminoalkyl

sats is, as additives for mineral bonds and modified in such a way that one is a

synthetic lubricating oils, greases, hydraulic copolymers of the designated type with one

Oils, power transmission oils, heating oils or gasoline. Aminoalkyl compound of the formula II at temperature

Ren from about 80 to about 200 ° C, preferably 100 to copolymers with the oil or synthetic 160 ° C, brings to reaction. If the graft copolymer lubricating oil is mixed and heated, advantageously the merisat contains building blocks which tend to aminolysis, pressure is reduced. You can do this at Temperaso it is advisable to work in the lower part of the door between 100 and 175 ° C and with mercury Temperature range, but carry out such a secondary pressure of a few millimeters, reaction does not reduce the value of the modi- The oil blends of the invention are produced,

celebrated graft copolymers for the purpose of by about 0.001 to 20 ° / ₀ of a oder'mehrere present invention. '. ■. ■ ·. of the amide-containing graft copolymer

The amount of the aminoalkyl compound is dissolved in the desired oil after the .merisate. The graft number the anhydride building blocks in the graft copolymer can be the only additive measured merisat. It can be from about 0.5 to about 2 mol or in conjunction with other known additives Aminoalkyl compound can be used for each anhydride group of the: for example antioxidants, Apply graft copolymer. Stabilizers,. anti-foam agents, agents

The reacted aminoalkyl compound can be used to improve the viscosity index or the pourability Remove filtration. 15 point, anti-corrosion agents, agents for · -her-.

The in this way modified graft mixed poly position an oily, means against wear and tear, against merisate can be viewed as oil-soluble products. Metal noises, for high pressures, rough cleaning .- .. in which units average on a base polymer and other known additives. As typi-, of maleamic or itaconamic acids or of any additions of this type are mentioned as examples Speaking amino acids of other unsaturated two-20 ^ '- methylene-bis ^ o-di-tert-butylphenol.Trialkylphebasic Acids are grafted on (amides or nol, tris (dimethylaminomethyl) phenol, phenothiazine, Half-amides of maleic acid, itaconic acid, etc.). The naphthylamine, N'-sec-butyl-N.N-dimethyl-p-pheny-T) Graft copolymers have grafted amidlenediamine, zinc, barium, nickel dialkyldithiophosphate * 'groups ,, which with a ketoimidazolinyl or phate, calcium, strontium, barium pefroleumsulfo-hexahydropyrimidylalkyl group are substituted. 25 nate, alkaline earth alkylphenates, alkaline earth salicylates, CaI-Es it has now been found that excellent oil ciumphenyl stearate, tricresyl phosphate, silicones; Mixed alkyl based on mineral oils or synthetic phenolalkylene oxide condensates, alkenylsuccinic acid lubricants Can be made by using re, sulphurized sperm oil and terpenes, poly isoin the same smaller amounts of one or more of the butylenes, polyacrylates, polydialkyl fumarate vinyl acetate, modified graft copolymers mentioned on- 30 copolymers of acrylates and polar monoliths. Various essential properties of the oils vinylidene compounds, such as N-vinyl-2-pyrrolidone, are thereby improved. The oil mixtures of Er vinyl pyridines, amino alkyl acrylates and methacrylates, Finding mean a considerable technical progress - polyethylene glycol acrylates.

step because the graft copolymers contained in them can be used as oil fractions of the mixtures of the invention

merisate more effective in various respects and 35 all lubricating oils or combustible oils mineral in the oils are more stable than those used according to the USA patent or synthetic origin. the font 2 980 652 copolymers produced. Viscosities of the lubricating oils on petroleum

The graft copolymers that form one component of the inventive oil mixtures, from the spindle oils to the engine oils, give aircraft engine oils to gear oils, and the mixtures have a good dispersing effect. In the 40 It can be about hydraulic oils, in the case of power transmission in the case of lubricating oils, this means that the sedimentation involves oils and fats. Synthetic lubricants and varnishes are prevented, while liquids, among other things, liquid esters, polyethers in heating oils and in oils intended for generating or transferring force, and silicones such as polyethylene glycol derivatives "provide stabilization against the ether or ester units in End position, further; / Formation of sludge and deposits reached 45 Esters, such as dioctyl sebacate or azelate, tributylphos will. In the oil blends of the invention, the phat, silicate esters are used. " In natural copolymers on which amide groups or synthetic lubricating oils modified to form amide groups, acid anhydride units according to the invention are grafted on, according to the proportion of modified graft copolymers, as dispersing and cleaning agent / merizate about 0.1 to about 10%, preferably 0.1 to zien graft copolymers can at the same time 50% _5:.: / '

the relationship between viscosity and temperature f ⁱ The following examples illustrate the improvement and, if necessary, the reduction of the molds of the invention. _; serve points. ^; -; in the case of "benzine, fuel oils ^ '. ■' ■ '■'"

and turbo oils are characterized by the mixtures of the er-; : '; \ : C ^ ¹ Iv Example 1 Finding through improved conductivity and safer 55 "^; .

Handling off. The graft copolymers with "^ A graft copolymers are produced by which the oil mixtures of the invention are produced 'rhah first cetylstearyl methacrylate, lauryl myristyl should be stored as concentrates and yer methacrylate (98 percent) in the ratio 90: 122 to send, so that they can be polymerized at their destination with about 70 ° / ₀ , then a mixture of liquids can be mixed in which they are to be used in a ratio of 6 ° maleic anhydride and ethyl acrylate. The graft copolymers can be polymerized out in a medium of white oil but also in a volatile solution;; A solution of the graft copolymer medium is dissolved, which is then added to a solids content of 30% with a little in oil. This volatile or non-volatile solvent has a viscosity of 99.degree 208 cSt. One can, for example, mix 450 parts of this in toluene oil solution of the graft copolymer in a lubricating oil merisate with 5 parts of N-j3-aminoethylethyleneurea, or a synthetic lubricant - stirred and heated under nitrogen for 4 hours by adding the toluene solution of the graft to 120 ° C a filter aid and filtered.

The grafted on anhydride units form acid The Panel Coker test is in the report of the 5th International

amide groups in which the amide nitrogen was recognized by the group at the Petroleum Congress 1959 (in an essay

■. ·. . ■ by R. M. J ο 1 i e) »Laboratory Screening Test for

.: ■ CH Lubricating Oil, Detergents and Dispersants «

. / ^{2 4} \ 5 wrote. A sample of the compound under test

-CH ₂ CH ₂ -N NH is dissolved in an oil, which 1 ° / _{0 of} a thermal

'.' .. ■ ^> ^ _Γ , ^ ' νU) contains unstable zinc dialkyldithiophosphate. Man

■ ..; .. ·. 1. · V brings the solution into a heated sump and

■ · ■■ · Il sprays for 2 hours at 290 ⁰ C against a heated one

■. ■ .-. O ίο sheet metal. One determines the weight gain of the

wearing. ■; , - sheet and compares with a blind test on oil

The oily solution of the modified graft copolymer without the substance to be tested.

merisats now has a viscosity of 99 ° C. The modified graft copolymer of the by-

305 cSt. : s: '. - '■■.' ., ■■■ · ■ ·: Spiels results in the Sundstrand pump test in a con-

Part of this solution is mixed with a concentration of 0.01 g in 100 cm ^{3 of} fuel 13 mg of solvent extracted midcontinent mineral oil sludge, while without the addition of 210 mg of sludge. . of viscosity 170 SUS One sets to 1 ° / ₀ mixed-be settled. . .
polymeric one. The viscosity is 6.53 cSt at 99 ° C. In the Sundstrand pump test, distilled propellant is 41.73 cSt at 38 ° C, viscosity index 117. A substance containing 4 g of synthetic sludge is mixed with another part of the oil concentrate moved to 20 addendum to be checked. The test oil is left with a neutral oil viscosity of 170 SUS. The solids content for 1 hour through a Sundstrand oil burner pump is 2 ° / ₀ . This mixture is dispersed asphaltene circulate containing a 100-mesh sieve, velvet melt with in the standard test both at 90 as at 150 ⁰ C., and then weigh the deposited sludge progressive dilutions, it is noted that (Osterhout and Schwindemart, Ing. Eng. Even with a polymer content of only 0.0625% as Chem., 48, p. 1892 [1956]).
both at 90 and at 150 ⁰ C 0.2 ° / ₀ asphaltenes

be dispersed. At 150 ° C even 0.4% Example 2

Asphaltenes dispersed. .

The modification of the anhydride building blocks with amino- Man polymerizes cetyl-stearyl methacrylate (98pro-

alkylalkylenharnstoff substantially increases the dispersants zentig 30) in the ratio 90: 122 to 73 ° / _0, resets

greediness. then a solution of 4.5 parts of maleic anhydride

A neutral oil with a viscosity of 100 S.U.S. has one in 85.5 parts of ethyl acrylate and polymerizes in

Pour point of 15 ° C. It is mixed with the oil content of white mineral oil. You get as

concentrate of this example to a solids content of starting material a 42.4 percent solution of a graft

1 ° / ₀ , the result is a pour point of - 32 ° C. 35 copolymers in oil with a viscosity of

An oil mixture with 1 ° / ₀ of this Pfropfmischpolymeren 3,536 cSt at 99 ⁰ C.

results in a machine test CR.C. FL-2 one To modify, 200 parts of this oily

Sludge value of 67.4 and a varnish value of concentrate with 2 parts of N- / 9-aminoethylethylene

15.1 for a total of 82.5. This oil contains urea, l- (2-aminoethyl) -2-imidazolidinone among

also 1% zinc dialkyldithiophosphate, and the oil is ^{heated to 120 °} C. for 5 hours with stirring. Man

this addition gives the values 46.8 and 7.4, which corresponds to a 43 percent solution of the modified one

corresponding to a total value of 54.2. Graft copolymer in which the basic

- The not yet grafted with N-jS-Aminoäthyläthylenhärn- carries the amic acid that carries with the

Substance converted graft copolymer results in 1% aminoethylethyleneurea was formed. The vis-

in the same oil mixture in the Fl-2 test a sludge viscosity in the mass is 510 oCSt at 99 ⁰ C.

value of 61.0 and a varnish value of 7.1. This is a mixture of 1% of this modified graft

Although 'already a considerable improvement of the copolymer in neutral oil 170 has at 99 ⁰ C a

Machine cleanliness, but the one with the modified viscosity of 7.72 cSt, at 38 ° C such of

The improvement achieved by the graft copolymer is still 55.4 cSt, corresponding to a viscosity index of 112.

more meaningful. . ■ 5 ° In the test against asphaltenes, the product is against

Per.FL-2 machine test, 0.2% asphaltenes in a concentration of 0.25%

a committee of the Coordinating Research Council both at 90 and 150 ° C and against 0.4% asphalt

iC.RC) for the investigation of fuels and tene in a concentration of 0.25% at 15O ⁰ C

oil running. A 6 cylinder chevro is allowed to operate. 1% of the modified graft copolymer

let engine for 40 hours with a certain 55 sats lowered in neutral oil a viscosity of

Fuel and the oil to be tested at a constant 100 SUS the pour point from 15 to -32 ⁰ C. *

Run load and speed. After this 0.01 g of the graft copolymer has expired in 100 ecm

Time the engine is dismantled and fuel oil turns out to be one in the Sundstrand pump test

rates the engine oils after deposits of sludge deposits of 41 mg compared to such

Mud and varnish. The maximum sum of loading 60 of 210 mg without addition. .

^ Ratings would be 100. · \,

An oil mixture with 1.4% of the modified graft example 3
Copolymers of the invention give a considerable reduction in deposits in the Panel Coker test. The deposit on the plate is 48 mg, while 65 game 2 of the same acrylates and methacrylates of the comparative experiment with the still unmodified a 30 percent solution of a graft copolymer of the same graft copolymer is a deposit of sats with grafted maleic anhydride units 78 mg results. , in oil with a viscosity of 264 cSt at 99 ° C.

■■ '. ■ ·. ■ ■ · ■■ ·· ·· ⁷ ' . . ' ■ ⁸ ■ '■■■ ■■■. ■ · ■

94.5 parts of this 30 percent solution are mixed with 24.5 parts of methyl methacrylate, together with initiator

with 0.66 parts of N-ß-Aminoäthyläthylenurea and and activator, heated for 5 hours to 105 bis

heated with stirring for 4 hours to 120 to 125 ° C. 110 ° C. and 2.5 hours to about 100 ° C. and diluted

The anhydride units are practically quantified in the reaction mixture with oil to a concentration

converted into acid amide units. The viscose 5 of 30% graft copolymer. The one so set

tat this modified graft copolymer in solution has a viscosity of 1.452 cSt at 99 ° C.

about 30prözeritiger oil solution is 350 cSt at 99 ° C. 141.6 parts of this solution are heated with 1.32 parts

A mixture of 1 ° / _{0 of} the polymeric aminoethylethyleneurea thus prepared was applied for 4 hours

sats in Neutralöl 170 has a viscosity of 150 ° C at 99 ° C and creates the reaction mixture by adding oil

6.84 cSt and at .38 ° C one of 43.56 cSt, corresponding to a concentration of about. 30% a. This

corresponding to a viscosity index of 121. At 99 ⁰ C, the solution has a viscosity of about

With a viscosity of 0.25%, das.Pro-200OcSt.

dukt both at 90 and 150 ° C 0.2% asphaltenes and. This disperses at a concentration of 0.25%

in a concentration of 0.5% at 150 ° C 0.4% modified copolymer at 90 and 150 ° C

Asphaltenes. The non-amidated graft copolymer 15 0.2% asphaltenes and in a concentration of

Merisat, on the other hand, requires a concentration of 0.5% at 150 ° C and 0.4% asphaltenes at 150 ° C. '.'. '.' ,

tion of 0.5 or 1%, to 0.2 or 0.4% asphaltenes The pouring point of a one percent solution of the

'to disperse. - · Modified polymer in neutral oil 100 is included

In neutral oil 100 the modified graft lowers -20.6 ° C.

copolymer has the pour point from 15 to - 29 ° C. 20 Example 7

Example 4 'In the starting product from Example 1, the

■. . . thylacrylate replaced by 81 parts of butyl acrylate .. The

. A according to Example 3, but with di-tert-butyl peroxide 30 percent solution of the starting product

as a catalyst at 110 to 115 ⁰ C, in the first phase 25 the graft copolymer in oil has a at 99 ° C

produced graft copolymer, which in 30pro viscosity of 216.5 cSt.

cent oil solution has a viscosity at 99 ° C. 207.2 parts of this solution are used for modification

3.230 cSt, serves as the starting product. 109.3 parts with 2.64 parts of N- / 3-Aminoäthyläthylenurea 4 hours.

this solution is heated to 120 to 130.degree. C. for a long time with 0.66 parts of N-ß-amino acids. Modified to 30%

Ethylethylene urea at 120.degree. C. for 4 hours has produced a copolymer which has been set at

heats and the oil solution of the modified graft at 99 ° C has a viscosity of 328 cSt.

mixed polymer to 30 ° / ₀ mixed polymer. A solution of 1% of this modified mixed polymer

represents. This solution 'has a viscosity of about merisats in neutral oil 170 has a viscosity at 99 ° C

4000 cSt at 99 ° C in bulk. of 6.62 cSt and at 38 ° C one of 42.04 cSt,

A mixture of this 35 diluted with lubricating oil corresponding to the viscosity index 119.

Concentrate dispersed at -90 and 150 ° C 0.2% Dispersed in oil at a concentration of 0.064%

Asphaltenes and in a concentration of 0.5% for the modified copolymer at 90 and 150 ° C

150 ° C 0.4% asphalts. 0.2% asphaltenes and at a concentration of

0.5% at 150 ° C 0.4% asphaltenes. That not mod-

, Example 5 40 fierte graft copolymer, however, requires a

: '' Concentration of 0.5% to get 0.2% asphalt at 90 ° C

To disperse a according to Example 2 to 4 with benzoyl peroxide as tene.

Catalyst at temperatures from 81 to 101 ° C. A solution of 1% in neutral oil 100 has a

The graft copolymer made has a 30 percent pour point of -29 ° C, which is a decrease of 14 ° C

oil solution at 99 ⁰ C has a viscosity of 1643 cSt. 45 corresponds.

For modification, .98.4% of this solution is added with. 'Example 66 parts of N - ^ - Aminoäthyläthylenurea ^{heated with stirring for 4 hours to 120 0} C .. The on a Man sets by the method of Example 1 from a concentration of 30% by adding oil, 90 parts of cetostearyl methacrylate, 120 parts of lauryl reaction product has in the mass at 99 ° C a 50 myristyl methacrylate and 15 parts of styrene in oil with a viscosity of about 1950 cSt. . Presence of Xymolliydroperoxyd as initiator and

• Didodecenyldimethylammonium chloride disperses as an activator in a concentration of 0.25%

modified graft copolymer both at 90 and a base polymer to which 9 parts of maleic

0.2% asphaltenes at 150 ° C. and grafted on in a concentrated acid anhydride in 66 parts of ethyl acrylate

tion of 0.5% at 150 ° C 0.4% asphaltenes. 55 to be. A 30 percent solution of this graft

/ ^; copolymer has a viscosity of 99 "C.

■ .. ^^ ■■■: ';^; :: ^; - ;? · _ν 'ί Example 6' 429cSt. . _: -; ■;

· - '■■ ■■..' ■■■ · "■ - · ^■;: ''.. ■■: '■ ■ ■ ··." ■■ -' Ά: '-' ■ ■ To Modification is heated. 120 parts of this

; For the preparation of the base copolymer poly solution for 3 hours at 140 "C with 132 parts,

A mixture of 153.5 parts of cetyl-60 N-Zi-aminoethyl ethyl alcohol is merized. A 3 () pio / entige

stearyl methacrylate (97.8 percent), 84.4 parts of lauryl solution of this modified copolymer has at

myristyl methacrylate (97.7 percent), 25 parts methyl- 99 ° C a viscosity of 762 cSt. ^: ·

Methacrylate and 15 parts of white Minenilöl with a cin percent solution in neutral oil 170 possesses

Diisopropylbenzene hydroperoxide as initiator and at 99 "C a viscosity of 6.99 cSt and at

Isooctylcrcsoxyäthoxyäthyldimethylbenzylammonium- 65 38 ° C one of 44.7 cSt, corresponding to the

chloride as an activator according to stage 1 of example 1 to viscosity index 122..

80%, then use a mixture of 4.5 parts of maleic in a concentration of only 0.063%, dispersed

acid anhydride, 13 parts of lauryl methacrylate and the modified copolymer at 90 and 15I) ¹ C.

■■■■ ^: "· '■' ■ ■" ■■■■ ^: ■ ·. ■ '■■ 209682/99

9 10

0.2% asphaltenes, in a concentration of 0.25 ° / ₀ 99 ° C a viscosity of 6.38 cSt and at 38 ° C a 0.4% asphaltene at 150 ° C. This is a considerable one of 40.54 cSt, corresponding to an increase in viscosity compared to the unmodified graft index of 116..
copolymer, which in a concentration of Example 11
0.125 ° / ₀ at 90 ° C, 0.3% asphaltenes and in a con-5

concentration of 0.5% at 150 ° C also only 0.2 ° / ₀ Asphal- According to the method of Example 10, polymerization is carried out

tene dispersed. a mixture of 30 parts of vinyl stearate and 5 parts

A one percent solution of the modified polyvinyl acetate sets a solution of after 2.25 hours

merisats in neutral oil 100 has a pour point of 7.5 parts of maleic anhydride in 13.5 parts of ethyl

- 32 ° C, corresponding to a lowering of the pouring point io acrylate and polymerized with the initiator and the

of 16.8 ° C. _ Activator of Example 10 in the presence of toluene as

Example 9 ~ Solvent for 8 hours. You dilute that

40.5 percent reaction mixture to a 30 percent

Polymerization is carried out according to the method of Example 8 in a solution in toluene which has a viscosity of 38.degree

a mixture of 210 parts of cetostearyl methacrylate, 15 of 62.7 cSt. . . :

285 parts of lauryl myristyl methacrylate, 90 parts of ethyl one mixes 50 parts of the 40.5 percent mixed poly

acrylate and 35 parts of oil up to 75% and polymerized merisate solution with 35 parts of neutral oil 100, stirred and

then further heated with the addition of a mixture of 14 parts to remove the volatile constituents

Maleic anhydride, 92 parts of ethyl acrylate and the temperature drives up for 1 storm at 5 mm / Hg

14 parts of N-vinyl-2-pyrrolidinone. A 30 percent 20 130 ° C and adds more oil to achieve a concentration

A solution of this graft copolymer in oil has to be set at a tration of 30% copolymer.

99 ° C a viscosity of 394 cSt. To modify it, 54.4 parts of this solution are heated

For modification, 84.2 parts of this oil solution and 0.66 parts of N - /? - aminoethylethyleneurea are heated

solution with 0.66 parts / i-Äminoäthyläthylenurea 4 hours at 120 ° C. This Reakttonsverbindungen

At 130 ° C. for 4 hours. A 30 percent solution 35 has a viscosity of 73.74 cSt at 99 ° C.

of the reaction product in oil has a mixture of 1% of the modified polymer at 99 ° C

Viscosity of about 2700 cSt. sats in Neutralöl 170 has a viscosity at 99 ° C

A one percent solution of the modified poly of 5.98 cSt and at 38 ⁰ C one of 37.82 cSt,

merisats in neutral oil 170 has a viscosity corresponding to the viscosity index 112 at 99 ° C.

tat of 6.93 cSt and at 38 ° C one of 48.45 cSt, 30 This disperses _{in a concentration of 0.063 ° / 0}

corresponding to a viscosity index of 108. modified polymer at 90 ° C. 0.2% asphaltenes

0.063%. of the copolymer dispersed at and in a concentration of 0.25% at 150.degree

90 and 150 ° C 0.2% asphaltenes and 0.125% with 0.4% asphaltenes. . .

150 ° C 0.4 »/« Asphaltenes. . . Eg spie 112 '

A mixture of 1% of the modified polymer 35 -

in neutral oil 100 shows a lowering of the pouring point. A mixture of 90 parts of cetyl-

11.2 ° C. stearyl methacrylate and 126 parts of isodecyl methacrylate

In the Sundstrand pump test, the modified 15 parts white mineral oil with diisopropylbenzene

Polymer the sludge deposit of the oil of 210 hydroperoxide and the activator from Example 10,

on 12mg. , '._. 40 sets a solution of after about 2.25 to 3 hours

Example 10 9 parts of maleic anhydride in 75 parts of ethyl

,. acrylate, together with further amounts of initiator, active

A mixture of 153.2 parts of vator and oil is polymerized, and the mixture is heated to 135 ° C. after 7.5 hours

Cetyl stearyl methacrylate, 96.7 parts of lauryl myristyl at 5 mm / Hg and diluted with 100 neutral oil

methacrylate and 15 parts of white mineral oil in a counter 45 percent concentrate of the graft copolymer

wart of Diisobutylphenoxyäthoxyäthyldimethylben- meren, which at 99 ° C has a viscosity of 432 cSt

zylammoniumchlorid as an activator and diisopropyl possesses. ,;,; /

Benzene hydroperoxide as initiator, then a mixture is used. 113.3 parts of this are heated for modification

mixed of 45 parts of methyl methacrylate and 10.2 parts, .. oily solution for 4 hours at 120 ⁰ C with 1.32 parts

Itaconic anhydride, together with another initiator 50 N-zS-Aminoäthyläthylenurea. ·.· The . Reaction and activator, and polymerize for 7 hours. mixed shows a viscosity of 1004 cSt at 99 ° C.

further. -. A mixture of 1% of the modified polymer

A 38.5 percent solution of the graft in neutral oil 170 S.U.S. has a viscosity at 99 ° C

copolymer in oil with a viscosity of 6.85 cSt and at 38 ° C a viscosity of 43.44 cSt,

360.2 cSt at 90 ° C. "55 corresponding to a viscosity index 122. ::

For modification, the mixture is heated with stirring at a mixture of 1% of the modified polymer

120 ° C for 4 hours 118 parts of this oil solution in neutral oil 100 has a pour point! Of -43 ° C,

0.66 parts / S-aminoethylethylene urea and filtered according to a reduction of 28 ° C. ■. -

the oily solution of the reaction product obtained,. This disperses at a concentration of 0.063%

using a silica-based filter aid. The 60 modified product at 90 and 15O ⁰ C 0.2% Asphalfiltrierte concentrate has a viscosity at 99 ° C tene and in a concentration of 1% at 150 ° C

from99cSt. . . ; .0.4% asphaltenes. -Ί, :.: ■ · -.- Jv ■■ ^: 'y'

0.063% of the modified copolymer dispersed ■■, ·, · ■ 'Example 13'

Yaw at 90 and 150 ° C 0.2% asphaltenes. ,. ,

A one percent solution of the modified poly 65 Man first polymerizes 35 parts of lauryl acrylate merisats in neutral oil 100 has a pour point of 25 parts of toluene, sets a solution of 1.5 parts

- 26.1 ° C, corresponding to a decrease of 11.2 ° C. Maleic anhydride in 13.5 parts of ethyl acrylate

A one percent solution in neutral oil 170 has on and polymerizes out. A 30 percent solution of the

Graft copolymer in toluene has a viscosity of 19.5 cSt at 38 ⁰ C. The copolymer is converted into oil according to the method from Example 12 and adjusted to a concentration of 30%. This solution has a viscosity of 97.3 cSt at 99 ^° C.

For modifying heating 40 parts of this oily solution for 4 hours at 12O ⁰ C and 0.53 parts of N-ß-Aminoäthyläthylenharnstoff. The reacted solution beitzt in the composition has a viscosity of 176 cSt at 99 ⁰ C.; ίο

A mixture of 1% of the modified polymer in Neutraiöl 170 has a viscosity at 99.degree of 5.93 cSt and at 38 ° C one of 38.15 cSt, corresponding to the viscosity index 109.

In a concentration of 0.063% the copolymer dispersed 0.2 ° / ₀ asphaltenes and at a concentration of 0.125% at 150 ⁰ C 0.4% asphaltenes at 90 ⁰ C. ; ^:

* Be is ρ ie 1 14 'For modification, a mixture of 220.2 parts of the 30 percent solution of the graft mixture polymer in the diester and 2.64 parts of N-ß-Am \ - noäthyläthylenurea 3 hours at 120 to 130 ⁰ C. The at 99 ⁰ C solution thus obtained has a viscosity of 167 cSt. :. '

By diluting with further amounts of di-2-ethyl-. Hexyl sebazate is a one percent mixture of the modified graft copolymer. It has a viscosity of 4.15 cSt at 99 ° C and at 38 ° C, 15.20 cSt, corresponding to a viscosity index of 196.. .

- This mixture was dispersed 0.2% asphaltenes at 90 smoothly and at 15O ⁰ C. '■ ·, ■ .-> -: =

B e i s ρ i e 1 16

One first polymerizes a mixture of

40 parts of cetostearyl methacrylate, 10 parts of lauryl

i \ 'j myristyl methacrylate and 12 parts of di-n-butyl itaconate

i- in toluene as a solvent and in the presence of 0.588 parts of tert-butyl perbenzoate up to about 80%,

Then uses a mixture of 3 parts maleic acid. anhydride and 35 parts of ethyl acrylate, along with additional amounts of catalyst and solvent and polymerizes until you get a 36.9 percent solution

the graft copolymers obtained. "In the setting 30 different amounts of this solution'des graft mixed poly-

to 30% polymer shows the toluene solution modified with merisats by dividing them into different

38 ° C a viscosity of 1600 cSt.

. ':. ^! A mixture of 90 parts of cetyl stearyl methacrylate, 120 parts of pure lauryl myristyl methacrylate and 15 parts of white mineral oil is polymerized according to the method of Example 15, in the presence of the initiator system from Example 1, sets according to the. Initial polymerization a mixture of 30 parts of methyl ethyl ketone, 30 parts. Maleic anhydride, 60 parts of n-butyl acrylate, together with initiator, activator and oil, polymerized out, stripped, the reaction mixture at 140 ° C / 5 mm Hg of volatile substances and receives a 30 percent solution whose viscosity at 99 ° C 103 cSt amounts to. According to the table below,

The volatiles at 130 ⁰ C / 5 mm Hg it drifts, transferred, as already described, the copolymer into oil and provides the oil solution for better handling a to a concentration of 20%.

For modification, 131.8 parts of this 20 percent solution, diluted with the same amount by weight of neutral oil with a viscosity of 100 SUS, with 1.32 parts of N- β -aminoethylethyleneurea are heated at 128 ° C. for 4 hours.

The modified graft copolymer possesses in a mixture of 1%. in Neutraiöl 170 at 99 ° C a viscosity of 6.75 cSt and at 38 ° C such a viscosity of 41.77 cSt, corresponding to the viscosity index 124. ·

In a concentration of 0.063% the copolymer dispersed at 90 and 15O ⁰ C and 0.2% asphaltenes at a concentration of 0.5% at 150 ⁰ C 0.4% asphaltenes. ' ■■: ■ / ■■ .- ·· ■ - ■ ;,

. B e i s ρ i e 1 15;

Conditions with / S-Aminoäthyläthylenharnston ^ hours heated ^{to 120 0 C.}

Implementation of graft copolymer and aminoethylethylene urea ..

Ver
search Parts by weight
solution Parts by weight
Urea derivative ■ MoI-
' ratio 1
2
3.
4th 122.8
123.3
123.1.
.126.4 1.32
1.85
2.64,
5.28 0.5
0.7
0.1
2.0

The molar ratio gives the ratio of aminoethylethyleneurea to the acid units determined by analysis. ,.

The reaction products of experiments 1 to 4 have the viscosities 1186 or 202.56 or 3490 or more than 2000 cSt. - ■■ ·. /:

All four test products disperse in a concentration of 0.063% at 90 and at

A mixture of 90 parts of cetostearyl methacrylate is first polymerized according to the above examples. 122 parts of lauryl myristyl methacrylate 55 150 ⁰ C 0.2% asphaltenes. Product no. 4 dispersed (98prozentig) in 15 parts and di-2-äthylhexylsebazat same concentration at 150 ⁰ C and 0.4% along with Diisopröpylbenzolhydroperoxyd

and

the quaternary ammonium salt of Example 1, sets; '.: later 9 parts of maleic anhydride and 81 parts of butyl acrylate and so much di-2-ethylhexyl sebacate that after the end of the 2-hour polymerization, 900 parts of a solution of the graft copolymer are present. At a concentration of 30%, the reaction mixture has a viscosity of 85 cSt at 99 ° C.

According to analysis, 2.94% building blocks of maleic anhydride are included in the reaction product. This is very close to the theoretical value of ^J / 0

Asphaltenes, while products No. 1 and 2 do so in a concentration of 0.25% and product No. 3 in a concentration of 0.125%. .

In a one percent mixture with oil, the viscosity index of products 1 to 4 is 118 or 119 or 117 or 130. ■ ■■■■; ■■

B e i s ρ i e 1 17

The method of Example 1 is used to polymerize cetyl stearyl methacrylate and lauryl myristyl methacrylate in a weight ratio of 30:40 in white mineral oil, then sets a solution of maleic anhydride

13 14

j. ■ '■ "■■"' ■ '-. ■ ■ ■

in butyl acrylate in a weight ratio of 3:27 and the reaction product obtained has acid amide polymerized further. At a concentration of 30% units that make up the group
of the graft copolymer, the reaction product has a viscosity of 151 cSt at 99 ° C. CH ₃ --CH - CH ₂

To modify it, 778 parts of this oil are heated

solution with 7.88 parts of N-ß-Aminoäthyläthylenharn-. .; -. HN-CH ₂ -CH-N NH

at 120 ° C for 4 hours. The reaction pro- '- ^ -. 1 .... T Λ'"· \ /

duct has a viscosity of 296 cSt at 99 ° C. ; ·; ! ■ !? 'ü .. ΓΐίΙΚίΠ' CH ₃ If '··. 9

For modification, a mixture is prepared at 55 ° C · ··: .- · .. ·. ·. ·. · .: ..., '' ■ '·' '. il

of 129.7 parts of the Lö- io - C produced in accordance with paragraph 1

solution, 1.57 parts of 1- (3-aminopropyl) -2-hexahydro- carry.

pyrimidinone and 8 parts of methyl ethyl ketone, stir, the viscosity in the mass at 99 ° C is 532 cSt.

heated for 4 hours to 120 ° C, whereupon 1 hour. The modified graft mixing described first

long at 130 ° C / 5 mm Hg, the reaction product has polymer in a mixture of 1% with oil

strips. -130 parts of an oil solution of a 15 are obtained at 99 ° C with a viscosity of 6.98 cSt and at 38 ° C a

Graft copolymer with acid amide units, wel- those of 44.31 cSt, according to the viscosity

che the group, 'index 123. ■' .. '·.

. ;.; ^: ; '";. 0.2% asphaltenes are mixed at 90 ° C with a

. ■ '■ .-. '..'. ' CH _2n concentration of 0.063% and at 150 ° C with a sol-

,. "" 20 particles of 0.125% dispersed. The final concentration

H ₂ C CH _{2 also} disperses 0.4% asphaltenes.

I! The modification described in the second place

- HN - CH ₂ CH ₂ CH ₂ - N NH i _ze t _g in a mixture of 1% in 100 neutral oil at 99 ° C

, \ / a viscosity of 7.08 cSt and such a viscosity at 38 ° C

■ '■' ■ C '25 of 44.08 cSt, corresponding to a viscosity index

• O disperses in a concentration of 0.063%

Product 0.2% asphaltenes at 90 and 150 ° C and wear. in a concentration of 0.025% at 150 ° C 0.4%

The bulk viscosity at 99 ° C is 783 cSt. 30 asphaltenes. -

In another embodiment, the third described modified Modify a mixture of 130 parts of the graft-graft mixed polymer possesses in a mixture of mischpolymerisats from paragraph 1 and 1.58 parts 1% in neutral oil 100 a viscosity of 6.81 cSt and 1 - (l-Methyl-2-artiinoäthyl) -5- methyläthylenurea at 38 ° C such of 43.52 cSt, corresponding to one and 10 parts of methyl ethyl ketone, stir through, 35 viscosity index 120.

heats to 130 ° C for 4 hours and strips by lightning a vacuum of 5 mm Hg. - the product discussed here.

Claims (1)

. The French patent specification 1166 507 describes patent claims: * grafts intended as additives to lubricating oils. merisate in which on a framework of polyisobutylene 1. Use of graft copolymers either an unsaturated organic ester or with a basic structure of at least one unsaturated hydrocarbon or an unsaturated alkyl acrylate or alkyl methacrylate, 'whose alkyl nitrogen-containing organic compound grafted on residues ensure oil solubility, with is on. ----- X ?. '· - ^: <"■''HH-;> - ■ ' ·. Grafted units of maleamine or itacone, on the other hand, are effiridally used as additives amic acid, the nitrogen atom of the acid to give technical oils graft copolymers with a the group io skeleton of at least one alkyl acrylate or alkyl .. A * methacrylate, the alkyl radicals of which are oil-soluble '/ \ ensure, and grafted units of MaIe- C _n H ₂₇ , N NH π) amine or itaconamic acid with a certain concentration \ / figuration used on the nitrogen atom. The inventive C 15 according to the oil additives used are in contrast to Il '. excellent dispersing properties for the known additives ¹ O medium, whereby the dispersing effect is relatively • moderately small additional amounts are achieved. . . /. In US Pat. No. 2,980,652 mixed carriers are described, in which A is an alkylene group with 2 or ao polymers for coating and impregnating 3 carbon atoms and η is a value for paper, leather, wood, glass, metal or the like , of 2 or 3, and the proportion of moles which are insoluble and therefore about 1 to 22 are out of consideration for the amine or itaconamic acid groups according to the invention. This preferably 2 to 11 percent by weight of the graft polymer is obtained by reacting 2-aminomiseh polymer, as additives for 25 alkyl-2-imidazolidines or hexahydro-2-pyromidone mineral and synthetic lubricating oils, lubricating with the carboxy functions one with maleic acid fats, hydraulic oils , Power transmission oils, heating anhydride, itaconic anhydride or a related oil or gasoline. Anhydride of an ethylenically unsaturated dicarbon 2. Use of graft copolymers made acid. ,. .
according to claim 1 in an amount of 0.1 to 10 percent by weight, based on the mixture. by delayed catalytic grafting of 3. Use of graft copolymers maleic anhydride, itaconic anhydride or ver 'according to claim 1 in an amount of 0.001 to equivalent anhydrides or mixtures of these ver-0 _? One percent by weight, based on the mixture, has already been proposed as a bond to an oil-soluble addition polymer for a liquid, combustible carbon. '. ·. Hydrogen according to claim 1. The graft copolymers used according to the invention merizates are made by grafting on maleic acid ".. anhydride, itaconic anhydride or the like Anhydrides produced on a base polymer. 40 This has one to ensure solubility . sufficient proportion in liquid hydrocarbons on long-chain groups. It's an implementation . with an aminoalkyl compound of the general The invention relates to the use of graft formula ^; copolymers with a basic structure of at least 45 A. at least one alkyl acrylate or alkyl methacrylate, whose ' X \ Alkyl residues ensure oil solubility, with - 'HNCH N NH m \ grafted units of maleamic acid (aminomalein- '- ^2. " ² " \ · y . " acid) or itaconamic acid, the nitrogen. ■. : λ: -; :: _^ν: -;. ' , -, C j ' atom of acid the group :: .50; .,. .; || ' _r . ■ '■' ■ ·. ·· ■ ■ ■, ■. ■: '. ■ .-. \ ' ^Γ ο ·. · ■ -'. ■. ■ ..'- ■ ^: ■ '-: