Polyalkenamine composition, intended for fuel or oil additive, method for its production; formulation of fuel, formulation of oil, and additives set, containing composition; and application of composition as additive in fuel formulations or oil formulations

FIELD: chemistry.

SUBSTANCE: polyalkenamine compositions, intended for fuel or oil additive, method for production of such additives, as well as formulation of fuel and formulation of oil, additives set, and application of such compositions as an additives, particularly as an additive for fuel cleanability improvement in injection systems of combustion engines with forced ignition. Polyalkenamine composition include at least one polyalkenamine in solvent, chosen from the group, containing components L1 and L2 mixture, where L1) represents at least one n- or iso-C10-C14-paraffin, and L2) represents at least one C10-C14-naphthene, L1 to L2 proportion being from 10:90 to 90:10.

EFFECT: improvement of polyalkenamine composition processing characteristics.

18 cl, 3 tbl, 3 ex

 

The present invention relates to polyalkenamers compositions intended as additives to fuel or lubricants containing at least one polyalkene in solvent with improved technological properties, in particular with improved low-temperature properties, to a method for producing such compositions, and to the composition of the fuel, lubricant and additive set containing these compositions and to the use of these compositions as an additive for fuel compositions or formulations of lubricants, in particular as additives for improved cleaning action of the fuel in the intake system of the engine internal sohraniia (DIC) with forced ignition.

The carburetors and the intake system of the engine with forced ignition (hereinafter carbureted engines), and injection system for dispensing fuel to a growing extent are impacted by pollution caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and fed to the carburetor exhaust gases of the housing of the crankshaft. These residues shift the ratio of air to fuel at idle and in the lower partial load range so that the fuel mixture is depleted, the combustion becomes incomplete and, on the other hand, increases the tsya fraction of unburned or partially burned hydrocarbons in the exhaust gas and increases the consumption of gasoline.

It is known that to prevent these disadvantages apply fuel additives to maintain the purity of the valves and carburetor, respectively, the injection gasoline engine (see, for example, the publication M.Rossenbeck in Katalysatoren, Tenside, Mineralöladditive", ed. J.Falbe, U.Hasserodt, p.223, publishing house of G. Thieme Verlag, Stuttgart 1978). Such surface-active fuel additives mainly referred to as "detergents". In the case of the composition of lubricants is often used so-called "dispersant" as surface-active additives, and they are also partly used as detergents in fuel compositions.

Polyalkaline belong to the most widespread fuel additives. They belong to the group of detergents and are characterized by excellent supporting clean or cleaning action on the engine, especially in the intake fuel systems engine.

From EP-A and ER-A known, for example, polybutyl and polyisobutylene, methods for their preparation and their use in compositions of fuel and lubricants. Thus, in this application, reference is made to the contents of these documents.

Polyalkenes, such as the above polybutene - or polyisobutylene usually get in the presence of an inert solvent, which after the reaction is not removed from the reaction smekal it does not interfere with the combustion process in the engine, he remains in the fuel insertion tool.

Conventional solvent polyalkenamers products problematic tolerate low temperatures. For example, they are prone to sedimentation when bicrystalline paraffin components of the solvent.

Thus, the objective of the invention is the development of new polyalkenamers compositions with improved low temperature properties.

The problem is solved polyalkenamers composica designed as an additive for fuel or lubricant containing at least one polyalkene in a solvent selected from the group comprising a mixture of components L1 and L2, where

L1 represents at least one n - or ISO-C10-C14-paraffin; and

L2 represents at least one10-C14-naphthene,

moreover, L1 and L2 are taken in a ratio of from 10:90 to 90:10.

Polyalkenoate part contained in the composition of polyalkenamers is a polymerization product of the same or different unbranched or branched monomers With2-C6-olefins, which are preferably statistically copolymerizable in the polymer.

Used to obtain polyalkenamers polyalkene has srednetsenovoj molecular weight Mn from about 200 to 10 000, for example from 500 to 5000, and the and from 800 to 1200, or from 850 to 1100, for example, 1000.

In a particularly preferred form of execution of the present invention polyalkene get from isobutene or Isobutyraldehyde Monomeric mixture such as a mixture of isobutene and approximately 20 wt.% n-butene. Preferably under polyalkenes mean polyisobutene (PIB).

In a further specific form of implementation of the invention polyalkene is polyisobutene (PROMINVESTBANK)obtained from polyisobutene, which has at least one of the following properties:

a) the content vinylidene double bonds is at least 70 mol.%, in terms of polyisobutene;

b) a polymer skeleton polyisobutene contains at least 85 wt.% isobutene units;

c) the polydispersity is from 1.05 to 7.

In particular polyalkene is a reaction product polyalkene and amine following General formula I

in which R1and R2independently from each other signify H, C1-C18-alkyl, C2-C18-alkanniny,4-C18-cycloalkyl, C1-C18-alcylaryl, hydroxy-C1-C18-alkyl, poly(oxyalkylene), polyalkyleneglycols or polyalkyleneglycol residue or together with the nitrogen atom to which they are attached, form heterotic the practical ring.

Used according to the invention PROMINVESTBANK is preferably the reaction product of hydroformylation reactive PIB, i.e. it has at least the above property (a), and subsequent reductive amination of exoproduct.

A significant advantage of the invention is that the composition of the solvent may contain technological solvent hydroformylation and subsequent reductive amination reactive PIB, without negative impact on the functionality of the additive.

Further particularly preferred form of implementation of the present invention relates to compositions containing PROMINVESTBANK in a mixture, which includes the above solvent, and the content of PROMINVESTBANK is at least about 63 wt.%, in particular, at least about 65 wt.%, for example from 65 to 99, or from 65 to 85, or from 65 to 75 wt.%, in terms of the total weight of the mixture.

Another object of the present invention are compounds of fuel or lubricants, in which the basic quantity of fuel or lubricants contains an effective amount of the composition according to the above definition. So, for example, fuel can be added to the composition according to the invention in quantities of from 10 to 10000, for example from 20 to 5000, mlnc lubricant composition may be added in an amount of from 1 to 15 wt.%, for example from 2 to 10 wt.%.

A further object of the present invention is the use of a composition according to the above definition as additives for compositions of fuel or lubricants, in particular the use as an additive to improve the cleaning action of the fuel in the intake systems of gasoline engines.

In addition, an object of the present invention is a set of additive (additive package)containing the above composition in combination with at least one spreadly.

The object of this invention is also the use of a solvent mixture of L1 and L2, as described above, to improve low temperature properties of PROMINVESTBANK.

A further object of the present invention is a method for polyalkenamers compositions according to the invention, and

a) polyalkene according to the above definition is dissolved in the above solvent;

b) the solution is subjected to catalytic hydroformylation in the presence of CO and H2; and

(C)exoproduct subjected aminating at hydrogenation conditions in the presence of an amine of the above formula I.

Preferably at the stage and receive a solution, dissolve the contents is of Italia which is not more than 40 wt.%, for example, <39 <35 wt.%, in terms of the total weight of the solution.

Unexpectedly it was found that the proper choice of solvent gives the opportunity to get polyalkenamers composition, which has significantly improved low temperature properties.

Such an improved low-temperature properties are expressed in a lower cloud point (CP), lower pour point (PP) and/or increased stability when stored at low temperatures.

Despite the change in the system of solvents unexpectedly found that when krupnoseriynom production there is no need to change existing production facilities or used catalysts. At the same volumetric flow of the present invention allows to obtain a significantly larger number is used as the additives of polyalkenamers. For the same amount of the additives used (polyalkene dissolved in the solvent) testing engine get significantly better results compared to the use of additives of the prior art.

Polyalkenamers the composition has at least one of the following low-temperature properties:

a) cloud point (determined according to DIN ISO 3015 or DIN EN 23015) less than or equal to -28� C;

b) pour point (determined according to DIN 3016) less than or equal to -27°C;

c) basically no deposition of crystals when stored at a temperature of from about -10 to -40°With, for example, at -30 or -35°C determined after storage for approximately the period of time from 1 day to 6 weeks, for example for 5, 10, 20 or 30 days.

Preferably the composition has a pour point of approximately -27 -55 to°With, for example, from -30 to -50°and/or turbidity of approximately -28 to -51°With, for example, from -33 to -45°C.

Preferably the density of the solvent (15°C, ASTM D 4052, EN ISO 12185-1996) is from about 650 to 900, for example from 720 to 820 or from 740 to 810 kg/m3and/or viscosity (20°C, ASTM D 445) of approximately from 1.0 to 5.0, for example from 1.6 to 2.0, or from 1.7 to 1.9 mm2/s

A) Polyalkenes

According to the invention in particular use such polyalkaline, polyalkenoate part which contains the polymerization product of the same or different unbranched or branched monomers With2-C6-olefins. Examples of such monomers are ethylene, propylene, 1-butene, isobutene, 1-penten, 2-methylbutane, 1-hexene, 2-methylpentane, 3-methylpentane, 4-methylpentan. This srednetsenovoj molecular weight Mn polyalkene is adapted is sustained fashion from 200 to 10 000.

Particular preference is given to polyalkenamers produced from polyisobutene. Particularly suitable polyisobutene are the so-called "highly reactive" polyisobutene, which are characterized by a high content of terminal double bonds. Under terminal double bonds while mean alpha-olefin double bond type

which is also called vinylidene double bonds. Suitable highly reactive with polyisobutene are, for example, polyisobutene that contain more than 70 mol.%, in particular, more than 80 mol.% or more than 85 mol.%, vinylidene double bonds. Preferred polyisobutene that have the same polymer skeletons. The same polymer skeletons have such polyisobutene that at least 85 wt.%, preferably 90 wt.% and most preferably 95 wt.%, consist of isobutene units. Preferably such a highly reactive polyisobutene have specified above srednetsenovoj molecular weight. In addition, the polydispersity of such highly reactive of polyisobutene can range from 1.05 to 7, in particular from 1.1 to 2.5, for example below 1.9 or below 1.5. Under the polydispersity understand coefficient srednevekovogo molecular weight Mw divided by srednetsenovoj mo is egularly weight Mn.

Particularly suitable highly reactive with polyisobutene are, for example, substances brand Glissopal BASF AG, in particular Glissopal 1000 (Mn=1000), Glissopal V 33 (Mn=550) and Glissopal 2300 (Mn=2300), and mixtures thereof. Other indicators srednecenovogo molecular weight can be set by known methods by mixing polyisobutene with different time intervals srednecenovogo molecular weight or by extractive preconcentration of polyisobutene certain intervals molecular weight.

Polyalkenoate components in a known manner is subjected aminating to obtain polyalkenamers.

While the preferred method for winning intermediate exoproduct by hydroformylation and subsequent reductive amination in the presence of a suitable nitrogen-containing compounds.

Suitable amines are, in particular, the compounds of formula I, i.e. HNR1R2.

R1and R2thus, independently of each other can mean:

(1) H;

(2) C1-C18is an alkyl residue; an example of such alkyl residues are unbranched or branched residues containing from 1 to 18 carbon atoms, such as methyl, ethyl, ISO - or n-propyl, n-, ISO-, sec - or tert-butyl, n - or isopentyl; in addition, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undeci is, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl and n-octadecyl, one or many times branched analogues; and corresponding residues, in which the carbon chain contains one or more ether bridges;

(3) (C2-C18-alkanniny balance; examples of suitable alkenyl residues are one or several times, preferably once or twice, unsaturated analogs of the above alkenyl residue containing from 2 to 18 carbon atoms, with the double bond may be in any position of the carbon chain;

(4)4-C18-cycloalkenyl the rest; as examples should be called cyclobutyl, cyclopentyl and cyclohexyl, as well as their analogues, substituted 1-3 C1-C4-alkyl residues; and C1-C4-alkyl residues selected from, for example, methyl, ethyl, ISO - or n-propyl, n-, ISO-, sec - or tert-butyl;

(5)1-C18-alcylaryl residue; and C1-C18is an alkyl group has the above values, and the aryl group is derived from a single - or dual-core condensed or unfused 4 - to 7-membered, in particular 6-membered, aromatic or heteroaromatic groups, such as phenyl, pyridyl, naphthyl and biphenylyl;

(6)2-C18-alkenylsilanes residue; and2-C18-alkene the other group and aryl group are the above values;

(7) hydroxy-C1-C18is an alkyl residue, and this residue corresponds to the analogues of the above C1-C18is an alkyl residue with one or more, preferably one terminal hydroxyl group; for example, 2-hydroxyethyl and 3-hydroxypropyl;

(8) if necessary, gidroksilirovanii poly(oxyalkylene) residue, which is obtained by alkoxycarbonyl N-atom 2 to 10 C1-C4-alkoxygroup, and to separate carbon atoms, if necessary, can be connected with the other hydroxyl group. The preferred alkoxygroup are methoxy, ethoxy - and n-propoxylate;

(9) polyalkyleneglycol the rest of the formula

Z-NH-(C1-C6-alkylene-NH)m-C1-C6-alkylen,

in which m denotes an integer from 0 to 5, Z denotes N or C1-C6-alkyl, C1-C6-alkyl means such remnants as methyl, ethyl, ISO - or n-propyl, n-, ISO-, sec - or tert-butyl, n - or isopentyl; and n-hexyl; C1-C6-alkylen means associated bridges analogues of these residues;

(10) polyalkyleneglycol the remainder consisting of 1-10 With1-C4-alkylamino groups, in particular ethylenimine groups;

(11) or together with the nitrogen atom to which they are attached, signify, in case the necessity is, substituted With 1-31-C4-alkyl residues 5-7-membered heterocyclic ring, which, if necessary, is another heteroatom in the ring, such as O or N.

Examples of such suitable compounds of the formula HNR1R2are:

- ammonia;

primary amines such as methylamine, ethylamine, n-Propylamine, Isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, hexylamine, cyclopentylamine and cyclohexylamine; and primary amines of the formula CH3-O-C2H4-NH2C2H5-O-C2H4-NH2CH3-O-C3H6-NH2C2H5-O-C3H6-NH2n-C4H9-O-C4H8-NH2, HO-C2H4-NH2, HO-C3H6-NH2and HO-C4H8-NH2;

secondary amines, such as dimethylamine, diethylamine, methylethylamine, di-n-Propylamine, Diisopropylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, dimentianon, digoxigenin, Dicyclopentadiene, dicyclohexylamine and diphenylamine; and secondary amines of the formula (CH3-O-C2H4)2NH, (C2H5-O-C2H4)2NH, (CH3-O-C3H6)2NH, (C2H5-O-C3H6)2NH, (n-C4H9-O-C4H8)2NH, (HO-C2 H4)2NH, (BUT WITH3H6)2NH and (HO-C4H8)2NH;

- heterocyclic amines, such as pyrrolidine, piperidine, morpholine and piperazine, and their substituted derivatives, such as N-C1-C6-alkylpiperazine and dimethylmorpholine.

- polyamine, such as, for example, With1-C4-alkylenediamine, di-C1-C4-alkylenediamine, three1-C4-alkylenediamine and higher analogues;

- polyethylenimine, preferably oligoanilines consisting of 1-10, preferably 2-6, ethylenimine units. Examples of suitable polyamines and polyimines are n-Propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, Diethylenetriamine, Triethylenetetramine and polyethylenimine, as well as the products of alkylation, such as, for example, 3-(dimethylamino)-n-Propylamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine and N,N,N',N'-tetramethylethylenediamine. Also suitable is Ethylenediamine.

C) Solvent

The solvent contained in the composition according to the invention, is a mixture of components L1 and L2, where

L1 represents at least one n - or ISO-C10-C14-paraffin, and

L2 represents at least one10-C14-naphthene,

moreover, L1 and L2 are taken in a ratio of from 10:90 to 90:10.

As examples of suitable arapinovich solvents, which do not limit the present invention include solvents, commercially available under the trade name MIHAGOL company BP Deutschland. In particular, we are talking about MIHAGOL M with the content of n-paraffin in it not less than 99 wt.%, a large part of the paraffins which has the length of the chain 11, 12 and 13 carbon atoms, and the other part consists of C14- and9-paraffins or paraffin with a shorter chain.

As examples of suitable naphthenic solvents, which do not limit the scope of protection of the present invention include solvents, commercially available under the trade name LIAV company FORTUM OIL AND GAS. In particular, we are talking about NESSOL LIAV 230, which mostly contains saturated cyclic aliphatic compounds, the number of carbon atoms is from 10 to 14.

Solvents or their mixtures are used in a quantity sufficient to give the composition described above, the preferred low-temperature properties.

(C) a composition

Getting polyalkenamers composition mainly corresponds to the synthesis of polyalkenamers. More detail can be illustrated by the example of the synthesis of polyisobutylene. Obtaining carried out as described in EP-A-0244616 or 0277345 method, which is here referred to.

To this end, polyisobutene in the presence of rhodium or cobalt is a new catalyst, such as decarbonylation rhodium, in the presence of CO and hydrogen is subjected to hydroformylation at a temperature of from 80 to 200°and pressure/hydrogen up to 600 bar, then perform amination of the resulting exoproduct (alcohol and/or aldehyde) in the hydrogenation conditions using the desired nitrogen-containing compounds, such as, for example, ammonia. Amination expediently carried out at a temperature from 80 to 200°C and pressures up to 600 bar. Before starting the reaction in polyisobutene add the solvent of the type indicated above in a quantity sufficient to obtain the necessary low-temperature properties of the final amine in the solvent.

D) Other additives

Polyalkenamers compositions according to the invention is added to the fuel or lubricants separately or in a mixture with other active components (apisalome).

As examples other than those described above polyalkenamers can be called the additive properties of the detergent and/or slow down the wear of the valve seats (below mentioned as additives detergents). This additive is a detergent contains at least one hydrophobic hydrocarbon residue, srednetsenovoj molecular weight (Mn) is from 85 to 20 000 and at least one polar group selected from these groups:

(a) the MES is - or polyaminopropyl, containing up to 6 nitrogen atoms, and at least one nitrogen atom has basic properties;

(b) nitro group, if necessary, in combination with hydroxyl groups;

(c) hydroxyl groups in combination with mono - or polyaminopropyl, and at least one nitrogen atom has basic properties;

(d) carboxyl groups or their salts with alkali or alkaline earth metals;

(e) the group of sulfonic acids or their salts with alkali or alkaline earth metals;

(f) polyoxy-C2-C4-alkylene group terminated with hydroxyl groups, mono - or polyaminopropyl, and at least one nitrogen atom has basic properties, or urethane groups;

(d) the group of esters of carboxylic acids;

(h) derivatives of succinic acid anhydride containing hydroxy and/or amino and/or amido-, and/or aminogroup; and/or

(i) the group obtained by the interaction Manniche substituted phenols with aldehydes and mono - or polyamines.

Hydrophobic hydrocarbon residue in the above-described additive is a detergent, which is responsible for sufficient solubility in the fuel, has srednetsenovoj molecular weight (Mn) of from 85 to 20 000, in particular from 113 to 10 000, preferably from 300 to 5000. Example of typical hydrophobic hydrocarbon mod is and, in particular, in connection with the polar groups (a), (C), (h) and (i) is polipropilenovyy, polybutylene and polyisobutylene balance, and Mn=300-5000, especially 500-2500, preferably 700-2300.

As examples of the above-described groups of additives such as detergents include the following.

Additives containing mono - or polyaminopropyl (a), preferable are polyalkene or polyalkenoate based on polypropene or conventional (i.e. mainly containing a double bond in the middle) of polybutene or polyisobutene with Mn=300-5000. If upon receipt of additives used polybutene or polyisobutene containing predominantly in the middle of the double bond (mainly in the beta and gamma position), the method of obtaining comprises the following steps: chlorination and subsequent amination or oxidation of the double bond with air or ozone to obtain the carbonyl or carboxyl compound, followed by aminating conditions recovery (hydrogenation). For the implementation of the amination can be used amines, such as ammonia, monoamines or polyamine, such as dimethylaminopropylamine, Ethylenediamine, Diethylenetriamine, Triethylenetetramine or Tetraethylenepentamine. Appropriate additives on the basis of polypropene described, for example, in WO-A-94/24231.

Other preferred sod is rashimi moneymakergroup (a) additives are products of the hydrogenation reaction products of interaction of polyisobutene with an average degree of polymerization P=5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as they are described in particular in WO-A 97/03946.

Other preferred containing moneymakergroup (a) additives are compounds derived from polyisobutene interaction with amines and subsequent digitalizacie and restoration of aminoalcohols, as they are described in particular in DE-A 19620262.

Containing nitrogroup (b), if necessary, in combination with hydroxyl groups of additives are preferably products of the interaction of polyisobutene average degree of polymerization P=5 to 100 or 10 to 100 with nitrogen oxides or mixtures of oxides of nitrogen with oxygen, as described in particular in WO-A 96/03367 and WO-A 96/03479. These interaction products usually are mixtures of pure Metropolitano (e.g., alpha-, beta-dinitroresorcinol) and mixed hydroxymetabolites (for example, alpha-nitro-beta-hydroxypropionate).

Containing hydroxyl groups in combination with mono - or polyaminopropyl (C) additives are, in particular, the interaction products polyisobutenylsuccinic derived from the containing predominantly terminal double bonds of polyisobutene with Mn=300 to 5000, with ammonia, a mono - or polyamines, as described in particular in EP-A 476485.

Containing carboxyl groups or their salts of alkaline or alkaline earth metals (d) Ricadi are essentially copolymers With 2-C40-olefins with maleic acid anhydride with a total molecular weight of from 500 to 20 000, a carboxyl group which is converted completely or partially into salts of alkaline or alkaline earth metals and the remaining balance of the carboxyl groups subjected to interaction with alcohols or amines. Such additives are known, in particular from EP-A 307815. Such additives serve mainly to prevent wear of valve seats and can with advantage be used, as described in WO-A 87/01126, in combination with conventional detergents fuel, such as poly(ISO)butanamine or polyetheramines.

Containing sulfopropyl or their salts of alkaline or alkaline earth metals (e) additives are mainly salts of alkaline or alkaline earth metal complex Olkiluoto ether sulfonterol acid, described in particular in EP-A 639632. Such additives serve mainly to prevent wear of valve seats and can be used in combination with conventional fuel detergents such as poly(ISO)butanamine or polyetheramines.

Containing polyoxy-C2to C4-alkylene group (f) additives preferably are polyethers or polyetheramines which can be obtained by the interaction of the C2up With60-alkanols, C6up With30-al is angiolo, mono - or di-C2-C30-alkylamines followed, C1-C30-alkylcyclohexanes or C1-C30-ALKYLPHENOLS with 1 to 30 mol of ethylene oxide and/or propylene oxide, and/or butilenica one hydroxyl group or amino group and, in the case of polyetheramines, subsequent by reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP-A 310875, EP-A 356725, EP-A 700985 and US-And 4877416. In the case of polyesters such products also have properties of oils-carriers. Typical examples are tridecanol or isotridecanol, isononylphthalate and polyisobutenylsuccinic and polyisobutenylsuccinic, and also the appropriate products of the interaction of ammonia.

The group containing esters of carboxylic acids (g) additives are preferably esters of mono-, di - or tricarboxylic acids with long-chain-alkanols or polyols, in particular those that have a minimum viscosity of 2 mm2/s at 100°With, as they are described in particular in DE-A 3838918. As mono-, di - or tricarboxylic acids may be used aliphatic or aromatic acid, as ester alcohols, respectively polyols are suitable, above all, long-chain compounds with the number of carbon atoms, nab is emer, from 6 to 24. Typical representatives of esters are adipate, phthalates, ISO-phthalates, terephthalate and trimellitate ISO-octanol, ISO-nonanol, ISO-decanol and ISO-tridecanol. Such products have the properties of oils-media.

Containing abstracted from succinic acid anhydride groups with hydroxy and/or amino and/or amido-, and/or kilograme (h) additives are preferably corresponding derivatives of anhydride polyisobutylenes acid, which is produced by interaction of conventional or highly reactive of polyisobutene with Mn=300 to 5000 with maleic acid anhydride by thermal or via the chlorinated polyisobutene. Particular interest are derived from aliphatic polyamines, such as Ethylenediamine, Diethylenetriamine, Triethylenetetramine or Tetraethylenepentamine. Such additives to gasoline fuel described in particular in US-A 4849572.

Containing the result of the interaction of manniche substituted phenols with aldehydes and mono - or polyamines group (i) additives are preferably products of the interaction polyisobutylene phenols with formaldehyde and mono - or polyamines, such as Ethylenediamine, Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine or dimethylaminopropylamine. Polyisobutenyl nesennye phenols can occur from conventional or highly reactive of polyisobutene with Mn=300 to 5000. Such "polyisobutene Mannich bases" are described in particular in EP-A 831141.

For a more precise definition of the individual here mentioned additives to gasoline fuel specifically referenced in the above documents prior art data.

Oil-carriers and other components

The composition of the additive according to the invention, moreover, can be combined with other conventional components and additives. In the first place should be called butter-media without expressed determinewhich properties.

Suitable mineral oils-carriers are fractions produced during the refining of oil, such as kerosene or naphtha, britstar or base oil with a viscosity of, for example, from the class SN 500-2000; and aromatic hydrocarbons, paraffin hydrocarbons and alkoxyalkanols. In addition, use the faction known as "hydrocracked oil released during the refining of mineral oil (fraction by vacuum distillation with a boiling range from about 360 to 500°product derived from mineral oils by catalytic hydrogenation at high pressure, isomerization, and deparaffinize). Also suitable are mixtures of the above mineral oil carrier.

Examples used according from what retenu synthetic oils-carriers are: polyolefins (poly-alpha-olefins or polyetheramine olefins), complex (poly)esters, (poly)alkoxylate, polyether, an aliphatic polyetheramines, initiated by the alkylphenol polyethers, alkylphenol-initiated the polyetheramines and esters of carboxylic acids and long-chain alkanols.

Examples of suitable polyolefins are olefinic polymers with Mn=400-1800, primarily on the basis of polybutene or polyisobutene (hydrogenated or digidrirovannye).

Examples of suitable polyethers or polyetheramines are compounds, preferably containing polyoxy-C2-C4-alkylene group, obtained by the interaction With2-C60-alkanols, With6-C30-alkanediols, mono - or di-C2-C30-alkylamines followed, C1-C30-alkylcyclohexanes or1-C30-ALKYLPHENOLS containing from 1 to 30 mol of ethylene oxide and/or propylene oxide, and/or butilenica on the hydroxyl group or amino group, and in the case of polyetheramines by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP-A-310875, EP-A-356725, EP-A-700985 and US-A-4877416. Examples of polyetheramines are poly-C2-C6-acceleratedin or their functional derivatives. Thus typical examples are tridecanol or isotridecanol, isononylphthalate is you, and polyisobutenylsuccinic and-propoxylate and the products of interaction with ammonia.

Examples of esters of carboxylic acids and long-chain alkanols are, in particular, esters of mono-, di - or tricarboxylic acids and alkanols or polyols with long chains, described in particular in DE-A-3838918. As mono-, di - or tricarboxylic acids can be used aliphatic or aromatic acids, and alcohols or polyols esters - long-chain compounds containing, for example, from 6 to 24 carbon atoms. Typical representatives of esters are adipate, phthalates, isophthalate, terephthalate and trimellitate isooctanol, isononanol, isodecanol and isotridecanol, such as, for example, di-(n - or ISO-tridecyl)phthalate.

Other suitable oil-carriers are described, for example, in DE-A-3826608, DE-A-4142241, DE-A-4309074, EP-A-0452328 and EP-A-0548617 that the proposal provides appropriate references.

Examples of particularly suitable synthetic oils-carriers are initiated alcohol polyesters containing from about 5 to 35, for example from 5 to 30, With3-C6-alkalinising units, such as propyleneoxide, n-butylaniline and ISO-butylaniline units or mixtures thereof. As examples of such initiator alcohols, is the quiet do not limit the scope of protection of the present invention, should be called long-chain alkanols or phenols, substituted long-chain-alkyl, and long-chain alkyl residue means, in particular, unbranched or branched C6-C18is an alkyl residue. Preferred examples are tridecanol and Nonylphenol.

Other suitable synthetic oils-carriers are alkoxysilane ALKYLPHENOLS, described in DE-A-10102913.6.

Other conventional additives are corrosion inhibitors, for example, on the basis prone to the formation of films ammonium salts of organic carboxylic acids or heterocyclic aromatics in the case of protection against corrosion of non-ferrous metals; antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine, or derivatives thereof, or on the basis of phenols, such as 2,4-di-tert-butyl-phenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid; demulsifiers; antistatics; metallocenes, such as ferrocene; tricarbonyl methyl-cyclopentadienylmanganese; substances to improve lubricity (lubricants), such as certain fatty acids, esters alkenylamine acid, bis(hydroxyalkyl) fatty amines, hydroxyacetamido or castor oil; and dyes (markers). If necessary, use tagelini to reduce the pH level of the fuel.

Components or additives can be added to fuel or lubricants, both individually and in the form of pre-prepared concentrate (additive package) together with polyalkenamers compositions according to the invention.

These detergent-additive containing polar groups (a)to(i)add in fuel, typically in the range from 10 to 5000 ppm by weight, in particular from 50 to 1000 ppm (by weight). The other components and additives, if necessary, added to the usual for this case.

E) Fuel and lubricants

The composition of the additives according to the invention can be used in all conventional fuels for gasoline engines, as described in Ullmann''s Encyclopedia of Industrial Chemistry, 5. ed. 1990, vol A16, s and trail. In addition, they can be used in diesel fuel, kerosene and jet fuel.

For example, perhaps the use of such compositions in fuel for gasoline engines with aromatic content not more than 60, for example not more than 42, vol.% and a sulfur content of not more than 2000, for example not more than 150 ppm (by weight).

The aromatic content in the fuel for engines with forced ignition is, for example, from 10 to 50, preferably from 30 to 42, vol.%, in particular from 32 to 40 vol.%. The content of the series is the fuel for engines with forced ignition is for example, from 2 to 500, preferably from 5 to 150, ppm (by weight), in particular from 10 to 100 ppm (by weight).

In addition, the fuel for engines with forced ignition may contain, for example, olefin in an amount up to 50 vol.%, preferably from 6 to 21 vol.%, in particular from 7 to 18 vol.%; benzene in an amount up to 5 vol.%, preferably from 0.5 to 1.0 vol.%, in particular from 0.6 to 0.9 vol.%, and/or oxygen in an amount up to 25 weight%, for example, up to 10 wt.%, preferably from 1.0 to 2.7 wt.%, in particular 1.2 to 2.0 wt%.

Especially worth mentioning is the fuel for engines with forced ignition, which simultaneously contains aromatic compounds in an amount of not more than 38%vol., olefin in an amount of not more than 21 vol.%, sulfur in an amount of not more than 50 ppm (by weight)benzene in an amount of not more than 1.0 vol.% and oxygen in the amount of from 1.0 to 2.7 wt.%.

The content of alcohols and ethers in gasoline fuel can be varied within a wide range. For example, the maximum methanol content typically is 15 vol.%, ethanol - 65 vol.%, isopropanol - 20 vol.%, tert-butanol - 15 vol.%, the Isobutanol - 20% vol. and ether containing 5 or more carbon atoms in the molecule, - 30%vol.

The steam pressure in the summer of fuel for gasoline engines is usually not more than 70 kPa, in particular 60 kPa (at 37°).

ROIG fuel for gasoline engine in the lei is as a rule, from 75 to 105. The range of appropriate MOC is from 65 to 95.

These specifications define conventional methods (DIN EN 228).

Examples of lubricants that add additives are oil and lubricants for vehicles or actuators, such as motor oil, transmission oil and turbine oil conventional composition and specifications.

The following examples in more detail describe the invention.

Experimental part

Example obtain 1

Getting polyisobutylene compositions with improved turbidity

In polyisobutene (PROMINVESTBANK), obtained according to EP-A-0244616 used in the example 1, the ratio of PROMINVESTBANK / solvent (at 62.5:37.5 weight. parts), add MIHAGOL M

In the same way we obtain the composition according to the invention, with a mixture of 66,7 parts PROMINVESTBANK and 33.3 parts MIHAGOL M

Measure the cloud point and pour point of the two compositions. The measurement results are shown below in table A.

Table a
The level of technologyInvention
The cloud point-27,6°-29,4°
Pour point-27°the -27°

Suddenly discovered that the composition according to the invention shows a significant improvement of cloud temperature.

Example of getting 2

Getting polyisobutylene compositions with improved low temperature properties

500 g of polyisobutene, molecular weight Mn is 1000, 269,2 g of solvent (80 wt.% MIHAGOL M and 20 wt.% LIAV 230), and 2.8 g of octacarbonyl cobalt for 5 hours, heated at 185°With a 2.5 l autoclave with lifting stirrer with stirring at 280 bar of CO/H21:1. The mixture is then cooled to room temperature, the catalyst was removed and 400 ml of 10%aqueous solution of acetic acid, and the mixture is washed until neutral. The resulting exoproduct for 5 hours, treated with 1 l of ammonia, 300 g of ethanol and 100 g of Raney cobalt in 5 l of a rotating autoclave at a hydrogen pressure of 200 bar and a temperature of 180°C. After cooling the mixture, the catalyst is filtered off, the excess ammonia is evaporated and the solvent is distilled off.

Used by polyisobutene is highly polyisobutene according to DE-A-2702604, which contains more than 70 mol. % of terminal double bonds.

Obtained in this way improved polyisobutene ("PROMINVESTBANK new content PROMINVESTBANK 65 wt.%) compared with known PROMINVESTBANK ("PROMINVESTBANK old"), obtained according to EP-A-0244616 (content is of PROMINVESTBANK 53 wt.%), on their pour point and stability when stored at a temperature of from -10 to -35°C. the Results are shown below in table C.

Thus, the product according to the invention is characterized by a significantly improved pour point, and stability during storage.

Example for the preparation of 3

Getting polyisobutylene compositions with improved low temperature properties

I repeat the example of getting 1, and the solvent used MIHAGOL M or LIAV 230 in different proportions. The ratio polyisobutylene polymer and solvent in the reaction product is 66:34. Measure the freezing temperature and the storage stability of the obtained product for different mixtures. The measurement results are shown below in table C.

Table
Ratio1)< / br>
MIHAGOL:LIAV
100:080:2070:3050:500:100
Pour point-27°-33°-36°-39°-51°
Stability when stored at -35°many crystalline depositslittle cu is starecheski deposits transparent liquidtransparent liquidtransparent liquid
1)the weight ratio

The results show that due to the variation of the solvent it is possible to achieve an unexpectedly significant improvement in stability during storage.

1. Polyalkenamers composition, intended as additives to fuel or lubricants containing at least one polyalkene in a solvent selected from the group comprising a mixture of components L1 and L2, where

L1 represents at least one n - or ISO-C10-C14-paraffin; and

L2) is at least one10-C14-naphthene, and L1 and L2 are taken in a ratio of from 10:90 to 90:10.

2. The composition according to claim 1, characterized in that polyalkenoate part of polyalkenamers is a polymerization product of the same or different unbranched or branched monomers With2-C6-olefins.

3. The composition according to claim 2, characterized in that srednetsenovoj molecular weight Mn polyalkene is approximately from 200 to 10000.

4. The composition according to claim 3, characterized in that polyalkene get from isobutene or Monomeric mixtures containing isobutene.

5. The composition according to claim 4, characterized in that polyalkene is the tsya polyisobutene.

6. Composition according to any one of claims 1 to 5, characterized in that polyalkene is polyisobutene obtained from polyisobutene, which has at least one of the following properties:

a) the content vinylidene double bonds is at least 70 mol.%, regarding polyisobutene;

b) a polymer skeleton polyisobutene contains at least 85 wt.% isobutene units;

c) the polydispersity is from 1.05 to 7.

7. Composition according to any one of claims 1 to 5, characterized in that polyalkene is a reaction product polyalkene and amine following General formula I

in which R1and R2independently from each other signify H, C1-C18-alkyl, C2-C18-alkanniny,4-C18-cycloalkyl, C1-C18-alcylaryl, hydroxy-C1-C18-alkyl, poly(oxyalkylene), polyalkyleneglycols or polyalkyleneglycol residue; or together with the nitrogen atom to which they are attached, form a heterocyclic ring.

8. Composition according to any one of claims 1 to 5,characterized in that as polyisobutylene use the reaction product of hydroformylation and subsequent reductive amination of the reactive polyisobutene.

9. The composition according to Liu the WMD one of claims 1 to 5, characterized in that the solvent is a process solvent hydroformylation and subsequent reductive amination of the reactive polyisobutene.

10. The composition is designed as an additive for fuel or lubricant containing polyisobutene in a mixture comprising a solvent according to the definition according to claim 1, and polyisobutene contains at least about 63 wt.%, in terms of the total weight of the mixture.

11. The composition of the fuel, in which the basic amount of the fuel additive contains an effective amount of a composition according to one of the preceding paragraphs.

12. The composition of the lubricant, in which the main quantity of the lubricant in the additive contains an effective amount of a composition according to one of the preceding paragraphs.

13. The use of a composition according to one of claims 1 to 10 as an additive for fuel compositions or formulations of lubricants.

14. The use of a composition according to item 13, characterized in that it is used as additives to improve the cleansing action of the fuel in the intake system of the internal combustion engine with forced ignition.

15. The set of additives containing composition according to one of claims 1 to 10, in combination with at least one spreadly.

16. The application of the MCA and solvents L1 and L2 according to the definition according to claim 1 for improving the low temperature properties of polyisobutylene.

17. The method of obtaining polyalkenamers composition according to one of claims 1 to 10, and

a) polyalkene according to the definition in one of claim 2 to 6 is dissolved in a solvent according to the definition according to claim 1;

b) the solution is subjected to catalytic hydroformylation in the presence of CO and H2; and

c) exoproduct subjected aminating at hydrogenation conditions in the presence of amine specified in paragraph 7 of formula I.

18. The method according to 17, characterized in that stage a) obtain the solution, the solvent content which is not more than 40 wt.%, in terms of the total weight of the solution.



 

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