DE1231374B - Use of graft polymers as a lubricant additive - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

ClOm

German class: 23 c -1/01

Number:
File number:
Registration date:
Display day:

1231374
Stl6685IVc / 23c
July 14, 1960
December 29, 1966

Graft polymers made from polyalkyl acrylates, vinyl, allyl or vinylidene monomers that are still polar Groups, e.g. B. carboxyl groups, sulfur, halogen are used as fat thickeners or known as protective colloids or paper coating agents.

It has now been found that an oil-soluble, basic nitrogen-containing graft polymer of 0.2 to 10.0 percent by weight of a basic nitrogen-containing, ethylenically unsaturated polymerizable monomer having 2 to 45 carbon atoms and a mixed polymer of aliphatic and aromatic vinyl compounds, which in a temperature range from 30 to 200 ⁰ C and has a molecular weight between 10,000 and 125,000, is suitable as a valuable multi-purpose additive for lubricating oils.

The particular effect of the graft polymers used according to the invention is that they contain no metallic components and therefore do not cause any deposits inside a machine and also represent ash-free dispersants, which at the same time keep cleanliness and improve the viscosity index of the lubricating oil.

The nitrogen-containing graft polymers whose preparation is not claimed, are prepared by polymerizing the nitrogen-containing monomers with the saturated Polymerisatgrundkörper at a temperature of about 30 to about 200 ⁰ C, preferably from about 60 to about 150 ⁰ C. The polymerization is carried out in the presence of free radicals as catalysts, t-butyl peroxide, benzoyl peroxide and azoisobutyronitrile being preferred. The amounts of catalyst are advantageously between about 0.1 and about 10, preferably between about 0.5 and about 5.0 percent by weight, based on the reactants. In order to obtain a product suitable as a lubricant additive, about 0.2 to about 10.0, preferably about 0.2 to about 3.0 percent by weight of the nitrogen-containing monomer, based on the total reaction mixture, should be used in the presence of a solvent.

The polymerization can also take place by graft polymerization of the nitrogen-containing monomer with the ozonized polymer base. Here, the Polymerisatgrundkörper in a suitable solvent, graft-polymerized with an approximately 0.1 to 6 ° / ₀ ozone containing gas. The nitrogen-containing graft monomer is subsequently reacted with the ozonated Polymerisatgrundkörper at a temperature of about 30 to about 140 ⁰ C. Use of graft polymers as
Lubricant additive

Applicant:

Standard Oil Company, Chicago, JIl. (V. St. A.)

Representative:

Dr. F. Zumstein, Dr. E. Assmann

and Dr. R. Koenigsberger, patent attorneys,

Munich 2, Bräuhausstr. 4th

Named as inventor:

Ellis Kirby Fields, Chicago, JIL;

Walter Collins Edmisten, Chicago Heights, JIl .;

Lawson Weston Mixon,

Hammond, Ind. (V. St. A.)

Claimed priority:

V. St. ν. America from June 14, 1959 (826 930),
dated July 20, 1959 (828 064)

Finally, the graft polymer with a solvent with low molecular weight, such as Methanol, ethanol, isopropanol, acetone, precipitated.

The graft polymers used according to the invention, which contain basic nitrogen, should have one Nitrogen content from about 0.01 to about 5.0, preferably from about 0.1 to about 1.0 percent by weight exhibit.

As a basic, nitrogen-containing, ethylenically unsaturated monomer, any polymerizable, preferably homopolymerizable monomers having from about 2 to about 45 carbon atoms, the at least containing a basic nitrogen group can be used. Such monomers include Dialkylaminoalkyl acrylates and methacrylates, ζ. Β. Dimethylaminoethyl methacrylate, diethylaminoethyl

ero 749/377

3 4

acrylate, dibutylaminoethyl methacrylate, diisooctyl- sator butyl peroxides used were then added

ammoäthylmethacrylat ^ ilaurylaminoätnylacrylatjDi- given, and the mixture was about 16 hours

octadecylaminoethyl methacrylate, vinyl-substituted he- heated under reflux. By adding a large

terocyclic compounds such as vinyl pyridines, ζ. B. Volume of methanol from the mixture was the

2-vinylpyridine, 4-vinylpyridine, 2-vinyl-5-ethylpyridine, 5 graft polymer precipitated. The graft polymer

N-vinalpyridine, N-vinylpyrrolidone, N-vinylpiperidone, was converted from hexane with methanol for purification

Amine-containing esters of unsaturated dicarbonic precipitates,
acids, e.g. B. Dialkylanünoalkylfumarate, -maleates,

-citraconates and -mesaconates and aminoalkylfuma-. .

rate, and other amino compounds such as N-methylol- io examples
acrylamide, N-methyl methacrylamide. Preferred

Monomers are those with at least one amino- A mixture of 995 g isobutylene and 185 g Substituted and advantageously dialkylaminoalkylacry-p-isopropyl-a-methylstyrene was ablated to -62 ° C and methacrylates. Cooling is particularly preferred and catalytic ^ for 30 minutes Dimethylaminoethyl methacrylate. 15 quantities of gaseous boron trifluoride passed through.

The isobutylene-p-isopropyl-a-methylstyrene obtained from a saturated hydrocarbon base

body existing polymer base body can be precipitated by mixed polymer with methanol and

Copolymerization from at least one mono- reprecipitated from xylene with methanol,

olefinic, ethylenically unsaturated, homopoly 50 g of the resulting copolymer were in

dissolved merizable hydrocarbon monomers with about 20 100 g xylene mixture. Then 8 g di-

2 to 6 carbon atoms with at least one aromatic methylaminoethyl methacrylate added, and the

table, homopolymerizable vinyl hydrocarbon mixture was heated to about 135 to 14O ⁰ C (Rücknuß-

material compound with at least 6 core carbon temperature of xylene) heated. Then Ig

atoms are produced, such monoolefinic t-butyl peroxide added and the mixture 16 hours

Monomers are, for example, isobutene and propylene, which are heated to reflux. The graft poly-

Ethylene, amylene, and the like, and preferably isobutene. merisat was used to remove the impurities

To the vinyl-substituted aromatic carbons - precipitated with methanol and from xylene with methanol

hydrogen monomers include styrene, p-isopropyl reprecipitated. The final product contained 0.29% by weight

«-Methylstyrene,« -methylstyrene, m-isopropyl-a-me- percent nitrogen,
ethyl styrene, vinyl naphthalene, and the like

merization takes place in the presence of an acidic. .

Catalyst such as tin (IV) chloride, aluminum bromide, example ό
Aluminum chloride, sulfuric acid, boron trifluoride

a temperature of about -73 to about -18 ° C. A graft polymer was formed by forming a The monomeric reaction mixture should form the mono- 35 polymer base, ozonize the polymer olefinic, Ethylenically unsaturated monomers in the base body and grafting of the basic stick one Molar ratio to the aromatic vinyl material-containing monomers prepared. The hermonomers from about 100: 1 to about 5: 1 distortion was done by mixing 10 weight holdings. In the polymerization conditions, isobutylene and 1 part by weight of styrene are present Polymer with a molecular weight of 40 is catalytic amounts of gaseous boron trifluoride about 20,000 to about 100,000. over 45 minutes at a temperature of

For use as lubricant additives, -6O ⁰ C. 16.5 g of the 10: 1 isobutylene obtained

the graft polymers according to the invention, molecular styrene copolymers, were dissolved in 350 ml of n-heptane

weights from approx. 10,000 to approx. 125,000 and pre-solved. The copolymer solution was with a

preferably from about 20,000 to about 70,000. 45 Oxygen stream containing 2 percent by volume of ozone

Such graft polymers are oil-soluble and treated at room temperature for 75 minutes. Of the

To improve the cleanliness and the viscosity index of the solution, about 0.18 g of ozone was absorbed. the

Lubricating oil. Solution was used to remove dissolved oxygen and

The following manufacturing instructions show the ozone being blown out with nitrogen for 20 minutes. she

Preparation of the basi- 50 used according to the invention was then carried out with 10 ml of freshly distilled

see nitrogen-containing graft polymers. ^ -Diethylaminoäthylmethacrylat treated and ^x / _a

Unless stated otherwise, percent means hour heated ^{to 88 to 92 ° C.} The obtained clear

Weight percent. Solution was made with 250 ml of methanol plus 100 ml

Treated acetone to make the graft polymer

. 55 cases. The graft polymer was made from 500 ml

Example 1 pentane with 500 ml of a 1: 1 methanol-acetone

Mixture reprecipitated and finally 3 hours for

A mixture of isobutylene and styrene heated in a devolatilization at 8O ⁰ C.

A molar ratio of 10: 1 isobutylene to styrene was obtained. The product obtained was 15 g of graft polymer. 30 minutes by catalytic amounts of gaseous 60 The graft polymer had a nitrogen content

Boron trifluoride at a temperature of about -57 to 0.15%. The average molecular weight

polymerized at about -68 ° C. The resulting mixing of the product was about 30,000.
polymer was cleaned. 100 g of the isobutylene-styrene copolymer were dissolved in 200 g of xylene

solved. 10 g of the dimethylaminoethyl methacrylate 65 Example 4
were added and the resulting solution became

to a temperature of about 135 to 14O ⁰ C (back A mixture of 10 parts by weight of isobutylene

temperature of xylene). 2 g of the catalyst and 1 part by weight of styrene was at -6O ⁰ C in an

Polymerized essence of catalytic amounts of gaseous boron trifluoride. 10 g of the formed Copolymer were dissolved in 320 ml of cyclohexane, and 3 ml of freshly distilled /? - diethylaminoethyl methacrylate were admitted. The resulting clear solution was in a ball mill for 36 hours bumped with pebbles. The solution was decanted from the pebbles, and the graft polymer was precipitated by adding 300 ml of methanol. The precipitated polymer became out 300 ml of cyclohexane reprecipitated by 300 ml of methanol. The polymer was then on for 2 hours dried in a steam bath. The yield was 8.7 g of colorless graft polymer. The graft polymer had a nitrogen content of 0.039 percent by weight. The average molecular weight of the product was about 20,000.

To detect for the viscosity index-improving properties of the graft polymer prepared above in Examples 1, 3 and 4 produced graft polymers in 2 ° / ₀ sodium concentration were prepared according to either a base oil A, which consisted of an extracted with a solvent SAE-10 mineral lubricating oil , or to a base oil B consisting of a solvent extracted SAE-30 mineral lubricating oil. Then, the viscosity index of the 2 ° / ₀ of 10 was determined for each composition and the viscosity index of each base oil as such as well as of each base oil compared: 1 isobutylene-styrene copolymer, with the aid of a boron trifluoride catalyst at -57 to -68 ° C, and to which no monomer was grafted with basic nitrogen. The comparative data are listed in Table I.

Table I. Viscosity
index composition 95 5
Base oil A, without additives Base oil A, containing 2% 10: 1 125 Isobutylene-styrene copolymer ...
Base oil A, containing 2% according to ₁₀ Example 1 manufactured product 126 Base oil B, without additives 89.5 Base oil B, containing 2% / ₀ 10: 1 Isobutylene-styrene copolymer ... 140.5 Base oil B containing 2 ° / ₀ in accordance with ₁₅ Example 3 manufactured product 131.5 Base oil B containing 2 ° / ₀ in accordance with Example 4 manufactured product 138.5

The dispersion and cleanliness qualities

ao of the polymers prepared above were tested by a carbon black suspension test and a Chevrolet engine cleanliness test checked. In the carbon black suspension test, according to the manufacturing instructions 1, 2, 3 and 4 manufactured products in comparison with the 10: 1 isobutylene-styrene copolymer and a 15: 1 isobutylene-p-isopropyl-6-methylstyrene copolymer tested as an additive at a concentration of 1.0 g in 80 ml of crude oil, that with 3 g of a paste of 20% carbon black was mixed in a heavy white oil. Each mixture was 5 minutes in one 100 ccm measuring vessel at room temperature (25 ° C) in a Herschel device to test demulsibility touched. The mixtures were then left to stand and tested for the tendency to build up soot.

The results are shown in Table II.

Table II

Additives

Tendency to deposit

None

10: l-isobutylene-styrene copolymer ..
15: 1-isobutylene-p-isopropyl-α-methylstyrene

Product of example 1

Product of example 2

Product of example 3

Product of example 4

deposited after 3 to 10 minutes
deposited after 3 to 10 minutes
deposited after 10 minutes
not deposited after 1 week
not deposited after 1 week
not deposited after 6 days
deposited after about 3 hours.

Engine cleanliness test

This test consists in applying a sample of the lubricating oil to be tested as a lubricant for 75 hours in a machine which has a single cylinder with a 9.65 cm bore and a 9.52 cm stroke and which operates at 3000 revolutions per minute and is operated at a load of 0 BHP (brake horsepower). The engine crankshaft has an annular mud trap that consists of a sharp indentation or "pocket" in the crankshaft. The sump temperature is 49 ° C and the outlet temperature of the cooling water 43 ⁰ C. As the fuel for the engine is a thermoplastic stabilized heavy crude oil with excessive inclination used to sludge formation. After 75 hours of continuous operation, the values for the lubricating oil are determined by dismantling the machine and determining the amount of sludge in the annular sludge trap that is fitted around the crankshaft and the amount of paint on the piston. Both values are on a 1 to 10 scale, with 10 being the theoretical best. The following samples were tested and the results are shown in Table III.

Sample A Solvent-extracted SAE-10 mineral lubricating oil.

Sample B = sample A, which contains 2 percent by weight of the above 10: 1-isobutylene-styrene copolymer.

Sample C = Sample A, which contains 2 percent by weight of the product of Example 1.

Table III

sample Sludge value Paint value A.
B.
C. 2.5 ¹ )
0.0
8.5 6, O ¹ )
5.5
5.9

*) Average of several tests.

As base lubricating oils, any lubricating oils, e.g. B. hydrocarbon oils can be used.

Various other known additives, e.g. B. antioxidants, antifoam agents, pour point depressants, EP agents, anti-wear agents, can additionally be contained in the above lubricating oils be.

Claims (1)

Claim: Use of an oil-soluble, basic nitrogen-containing graft polymer from 0.2 to 10.0 percent by weight of a basic nitrogen-containing, ethylenically unsaturated polymerizable Monomers with about 2 to 45 carbon atoms and a mixed polymer of aliphatic and aromatic vinyl compounds operating in a temperature range of 30 to 200 ° C was obtained and has a molecular weight between 10,000 and 125,000, as a lubricant additive. Considered publications:
German Auslegeschriften No. 1 014 694.1 015 226, 024 240, 1118 971, 1138 492. When the registration was announced, two priority documents were displayed. 609 749/377 12.66 © Bundesdruckerei Berlin