DK144336B - ACID NUTRALIZING LUBRICANT - Google Patents

Description

(19) DENMARK {É?) § \ Ra / o «PRESENTATION WRITING ου 14U336 Β

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. 240 ^ / 71 (51) lnt.CI.3 C 10 M 1/20 (22) Filing Day 18 May 1971 C 10 M 1/38 (24) Running Day 1 8 May 1 971 (41) ) Aim. available Nov. 20; 1971 (44) Presented February 22. 1982 (86) International Application No. - (86) International Filing Day - (85) Continuation Day - (62) Master Application No. - (30) Priority 19 May 1970, 24825/70, IT (71) Applicant AGIP SPA, 72 Rome , IT.

(72) Inventor Brunello Ciuti, IT.

(74) International Patent Office.

(54) Acid neutralize end lubricant.

The invention relates to an acid neutralizing, antacid, lubricant suitable for use in ship machinery.

It is known that lubrication in the open circuit of the cylinders in large, slow, two-stroke ship engines has for many years been based on the use of "antacid oils", characterized in that they contain a very large amount of additives, that is, in on the order of 25% by weight or more.

The reason why these oils are used lies in the fuel used. To reduce the operating costs of the machines, the heavy fuel with Q is supplied with a high content of sulfur. Obviously, under these conditions, acidic combustion products, in the main sulfuric acid, must be neutralized so that they do not get

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q time to corrode the metal of the cylinder housing with which they come into contact, ί Although the neutralizing function is apparently the main function of these oils, it is important to remember that the oils must simultaneously act as lubricant and detergent, because the machine mud and thermal degradation products of the fuel and of the lubricant itself must not be able to be collected and deposited in places where there is a need to maintain free movement between the mechanical parts.

The most critical zone from this point of view is the piston ring grooves, where as a result of the presence of varnish and tar products resulting from the decomposition it is possible that the piston ring is blocked either completely or only partially. In this case, the piston ring cannot perform its sealing effect and is therefore more affected by mechanical stresses.

It is known that one drawback, which is often encountered by many common acid neutralizing oils due to their high content of additives, is the formation of large amounts of residual substances which originate from the additives.

The amount and physical condition of these residues can affect the operation of the machine as the opening, washing and outlet valves can be clogged by hard material which is difficult to remove.

The hardness and nature of the oil residues, together with the physical properties of the fuel, can cause wear and tear on the piston skirt, on the sterile bead ring and on the cylinder housing.

Heavy fuel with a fairly low sulfur content (up to a maximum of 1%) has recently been obtained using special raw materials. These fuels have been found to be incompatible with lubricating oils with a high total base oil, causing wear and combustion under special operating conditions of the machine. It can be seen from the foregoing that an acid neutralizing oil should comprise an appropriate combination of ingredients, each having a specific function and not impairing the other components' functions, but if possible on the contrary, improving upon them.

In terms of the deterrent function, the additives in acid neutralizing oils for ship engines are very similar to the additives for oils for machines with less cylinder capacity. The neutralizing function usually arises from calcium or magnesium salts of organic acids or of weak inorganic acids.

It is known in the manufacture of complex and balanced additives for acid neutralizing oils to use overbased calcium sulfonates of natural or synthetic origin (alkarylsulfonates) which contain calcium as a fine dispersion of calcium carbaminate. The dispersion obtained is such that the product seems to be completely dissolved in the oil, and it is also apparently soluble in most known organic solvents. The preparation process for such dispersions is well known and involves either the use of calcium derivatives of phenols or of sulfophenol complexes which are themselves also anticorrosive agents and, when converted into appropriate salts, also act as detergents and dispersants.

3 144336

The invention is intended to provide an acid neutralizing lubricant for lubrication in an open circuit in the cylinders of large, slow, two-stroke ship engines in such a way that the deterrent, neutralizing and lubricating properties of the oil are better balanced than in known lubricants for this purpose as discussed above. and that the agglomerated residues become sufficiently brittle and easily removable.

The lubricant according to the invention contains: a) at least one compound selected from esters and alkaline earth metal salts of organic acids; and d) an ashless detergent and dispersant, and it is peculiar that the ashless detergent and dispersant is either a polymer having a molecular weight between 1000 and 3000 of general formula I (see claim) wherein R is an alkyl group or a hydrogen atom, X is an oleophilic group selected from carboxyl groups attached to alkyl groups of 4 to 40 carbon atoms, and Y is a polar group selected from the following: - C - (0 - R ') - CH - P1

2 n-r ') - N

11 \ R2 S S x V> "\” c \ / r1 - <r

NHR xo-r'-n XO- (r'-O) -ribH

\ n

V

~ y - oh

N

R 1 - NH - Ε * 0Η 1 2 in which polar groups R, R and R are hydrogen or alkyl groups having from 4 to 40 carbon atoms, R 'is an alkylene group and n is in the range of 1-10, or has the general formula II (see claim) wherein R and R 'have the meaning given above and x is in the range 2-10.

Detergents and dispersants of these types are known for use in smaller machines; it has been found in accordance with the invention that their deterrent effect synergistically adds to the action of the aforementioned sulfonates * phenates and sulfophenates.

The organic acids mentioned under a) above are preferably selected according to the invention from the class of saturated and unsaturated organic acids and aliphatic monocarboxylic hydroxy acids containing 10 to 30 carbon atoms.

Esters derived from said acids include ethyl, propyl, isopropyl, butyl, arnyl, oleyl, stearyl, palmityl, glycerol (mono, di and tri) and ethylene glycol (mono and di) esters.

The dispersing neutralizing compounds mentioned in (b) are used in such an amount as to ensure a good neutralizing effect at the same time as the antioxidant and anti-corrosive action.

The molecular weight of the alkaryl sulfonates which are most suitable for the delivery of calcium derivatives and which are capable of being efficiently distributed to stabilize a very large overbase is in the range of about 500th

The most effective sulfophenates for use according to the invention are characterized in that they have in the molecule two aromatic nuclei bonded together by one or more sulfur atoms, and that they have the general formula: 0-vr-o where R and R various alkyl groups having from 4 to 20 carbon atoms, M is an alkaline earth metal atom, and n is an integer between 1 and 10.

While the sulfur increases the anticorrosive properties of the sulfophenate, the length of the side chains may affect the solubility of the products.

Phenols which can be used with particular advantage according to the invention may be the most simple of the formula R - - OH, wherein R is alkyl of from 4 to 40 carbon atoms, which phenols may have different substituents in the nucleus or consist of two or more nuclei and having substituent chains bonded together e.g. at hydrocarbon bridges.

The polymeric ashless dispersing and degreasing agents of formula I can be obtained from a large number of monomers which can provide a structure for ensuring solubility in the oil, e.g. esters of acrylic and methacrylic acids, esters of polycarboxylic unsaturated acids (maleate, fumarates, itaconates), vinyl and allylic esters.

The polymeric detergents and dispersants of formula II are, as will be seen, alkenyl-N-substituted succinimides.

The alkenyl succinic acid is obtained by condensation of an olefin polymer, usually a polyisobutylene having a molecular weight of 800 to 1200, and maleic anhydride.

5 144336

The order in which the various components are added is usually of little importance and is regulated on the basis of the characteristics and operational capabilities of the system at hand. It is necessary to be particularly careful when using acidic substances with sulfonates and overbased sulfophenates, as the amount of calcium contained therein, in the form of salts of weak organic acids or of carbonic acid, can be moved and can be bound to the added acid. , which gives rise to the formation of a new compound which does not always have satisfactory solubility or the possibility of dispersion.

In the case where free organic acids are used and where neutralization thereof is necessary, this operation is usually carried out for approx. 1/4 of the mineral oil by adding the required amount of calcium oxide together with the acidic substance by vigorous stirring by means of a turbine stirrer and by adding the necessary amount of water. The product is heated and stirred in a temperature range between 70 ° and 110 ° C for a period necessary to remove the water which has been added and to complete the reaction.

Other ingredients are added to the product thus obtained at temperatures usually used for simple mixing operations.

The ratio of the components of the present lubricant may vary within a very wide range depending on the field of application in which the lubricants are to be used. In most cases, the agent may advantageously contain from 2 to 15% of component a), from 2 to 40% of component b), from 0.01 to 10% of component d), the remainder consisting of synthetic or mineral lubricating oil.

The invention is further explained by the following examples.

Example 1

Overbased calcium sulfonate of sulfonic petroleum acids (average molecular weight: about 470) (content of active amount: 50-555o) (total base number, TBN, 270 mgKOH / g of the sample) 20% by weight "Commercial grade" ethyl oleate 4% by weight "Commercial grade "Polyalkenylsuccinimide based polymer dispersant (molecular weight about 1000) 2% by weight

Mineral oil (V.I., Viscosity Index, about 90, E.V.,

Angels viscosity at 50 ° C, 17-18) 74% by weight

The product has the following main characteristics: 6 U / 4336

Appearance clear

Color brown E.V.50 18.5 V.l. 80 T.B.N. (mg KOH / g) 55.57% by weight.

Example 2 "Commercial" overbased calcium sulfophenate T.B.N. about 260 mg KOH / g 18 wt%

Barium stearate 5% by weight

Synthetic neutral calcium sulfonate having a molecular weight of 500 3 wt% Commercial dispersant detergent based on polyalkenylsuccinimide 2 wt%

Mineral oil, V.l. = 70 E.V. = q 72% by weight,

The product has the following characteristics:

Appearance opalescent

Color dark brown E.V.5q 20.5 V.l. 65 T.B.N. 45

Example 3

Synthetic overbased calcium sulfonate having a molecular weight of approx. 550 and a T.B.N. = 300 mg KOH / g 22 wt%

Stearylpa feita-t 6% by weight "Commercial" dispersant detergent based on molecular weight polyalkenyl acrylamide 2000 - 3000 2% by weight

Mineral Oil, E.V. ^^ - 19, V.l. = 90 70% by weight

The product has the following main characteristics:

Appearance opalescent

Color dark brown E.V.50 20.5 V.l. 80 T.B.N 65 144336 7 F-xanpel 4 "Commercial" overbased calcium sulfonate having a molecular weight of approx. 480, prepared from synthetic sulfonic acids, T.B.N. of approx.

300 mg KOH / g 22 wt%

Isopropylurate 7% by weight.

"Commercial" neutral calcium sulfonate having a molecular weight of approx. 420 2% by weight "Commercial", polymeric ashless dispersant based on polyalkenyl acrylamide, molecular weight 2000 - 3000 1% by weight

Mineral oil, E.V. ^ q = 18, V.I. = 90 68% by weight,

The product has the following main characteristics:

Appearance clear

Color dark brown E.V.50 20.5 V.I. 85 T.B.N. 65

Example 5 "Commercial" overbased calcium sulfophenate prepared from petroleum having an average molecular weight of 470, T.B.N. = 300 mg KOH / g 20% by weight

Amyl hydroxystearate 6% by weight

Neutral barium sulfophenate derived from "commercial" nonylphenol 3% by weight "Commercial" dispersant based on polyalkenylsuccinimide with a mean V.I. 1% by weight

Mineral oil, E.V.50 = 17, V.I. 85 - 90 70% by weight

The product has the following main characteristics:

Appearance clear

Earve dark brown E * V'50 17 V.I. 80 T.B.N. 60 8 144336

Example 6 "Commercial" neutral calcium sulfophenate consisting of two molecules of nonylphenol bonded with a sulfur bridge between the cores and neutralized with calcium, T.B.N. = 140 KOH / g 5% by weight "Commercial" overbased calcium sulfophenate of the same structure as before, but containing

CaCO 2 as a fine dispersion, T.B.N. = 250 mg KOH / g 20% by weight "Commercial" oleyl oleate 7% by weight "Commercial" ashless detergent and dispersant, based on polyalkenylsuccinimide 1% by weight

The mean V.I. mineral oil 67% by weight.

The product has the following characteristics:

Appearance clear

Color dark brown E.V.50 18 V.I. 70 T.B.N. 60

Example 7 "Commercial" over basic calcium sulfophenate derived from petroleum, average molecular weight 470, T.B.N. = 250 mg KOH / g 25 wt% Commercial calcium oleate 5 wt%

Dispersant based on polyalkenylsuccinimide 3 weight-4

Medium-grade mineral oil V.I. 67% by weight

The product has the following main characteristics:

Appearance clear

Color dark brown E * V * 50 19'5 V.I. 80 T.B.N. mg KOH / g 63

In order to develop the characteristics of acid neutralizing oils for use in ski machines, it is known that long and laborious tests are needed, which must mainly be performed on machines installed on board the ship and in more fortunate cases in thermoelectric systems. It is known that these large machines are unfortunately subjected to a considerable number of different conditions during normal operation, which makes it difficult to interpret the test results. Additional difficulties are linked to logistical and financial considerations. Therefore, it is usually not possible to make an initial assessment directly using the machine, but laboratory equipment is used which is suitable for the largest

Claims (1)

9 144336 possible duplication of the conditions arising from practical use. Only after a long and careful assessment work in the laboratory, the agent according to the invention has been used for tests on machines installed on tankers using groups of two to three cylinders of the same machine, so that several tests can be performed at the same time. After approx. One year of testing, during which the machine worked almost continuously (approximately 7500 hours of operation), the machine has been inspected under normal inspection. The results obtained with the lubricant according to the invention were very satisfactory as shown in the following table: Wear of piston skirt 0.05 mm / 1000 hours Piston rings (fracture) 10% Fixed of piston ring of no practical importance Outlet valves maximum clogging 10% average clogging for each valve 5 % Wash valves maximum clogging 10% average clogging for each valve 5% Acid neutralizing lubricant containing: (a) at least one compound selected from esters and alkaline earth metal salts of organic acids; c) a synthetic or mineral lubricating oil, and d) an ashless detergent and dispersant, characterized in that the ashless detergent and dispersant is either a polymer having a molecular weight between 1000 and 3000, of the general formula I: “Rr RRRH — c - CH 2 - c - CH 2 - c - ch 2 - Ϋ - CH 2 - C - CH 2 - H in _x XYXX Jp where R is an alkyl group or a hydrogen atom, X is an oleophilic group selected from carboxyl groups attached to alkyl groups having 4 to 40 carbon atoms, p is an integer of such size that the molecular weight is as given, and Y is a polar group selected from the following: