CN1780809A - Production of diphenylamine alkylated with olefin mixtures - Google Patents

Abstract

Disclosed herein is a process for the preparation of alkylated diarylamines comprising adding said diarylamine an olefin mixture containing highly reactive fractions, as well as fractions exhibiting a relatively lower chemical reactivity, in the presence of an acidic clay catalyst at a temperature low enough to prevent substantial deactivation of the catalyst until the addition is complete and then increasing the temperature to increase the alkylation rate of the less reactive fractions.

Description

Produce the method for alkylated diphenylamine

According to the 35th right of United States Code § 120, the present invention requires the right of priority of the U.S. Provisional Application No.60/459973 that is entitled as " DIPHENYLAMINE ALKYLATED WITH OLEFIN MIXTURESCONTAINING FRACTIONS WITH VARYING DEGREES OF ACTIVITY " of submission on April 4th, 2003.

Background of invention

1. invention field

The present invention relates to the mixture of alkylated diphenylamine, this preparation process of mixture and its as additive in order to the stable purposes that is easy to the organic products of oxidation, heat and/or photoinduction degraded.This additive can be joined widely used many organic productss in engineering, for example in lubricant, hydraulic fluid, metal working fluid, fuel or the polymkeric substance, to improve its performance properties.

2. the explanation of association area

U.S. Patent No. 2943112 has been described from the antioxidant in the alkylated diphenylamine group, and described alkylated diphenylamine is by in the presence of as the mineral acid of catalyzer and a large amount of acid clays, makes pentanoic and olefine reaction and prepares.The mixture that causes generating monoalkylation and dialkylated diphenylamine with the olefin alkylation diphenylamines.In the method, a large amount of relatively parent materials, not reaction of the pentanoic of 6-12% usually, the anti-oxidant usefulness that this has reduced alkylated diphenylamine causes sludgy deposits, and has given product non-required toxicity.Proposed will with extra olefine reaction replacement scheme as fractionation by distillation parent material from product.

U.S. Patent No. 3496230 has been described in the presence of aluminum chloride type Friedel-Crafts catalyst, the mixture for preparing 80% dinonyldiphenylamine and 15% nonyl diphenylamine, but this mixture still has 2% pentanoic content (referring to the embodiment 2 of this patent).As shown in the U.S. Patent No. 6315925, the preparation of this mixture is unfavorable especially, because it by the chlorine of trace, metallic compound and non-required by product (for example, the alkylating pentanoic of N-and in 2-and 2 '-position by alkylating pentanoic) pollute, its color is black and unusual thickness.

U.S. Patent No. 4824601 discloses by making the method for pentanoic and diisobutylene reaction production fluid body anti-oxidant compositions in next life, soil (earth) catalyzer that this method is included in acid activation exists down, make pentanoic and diisobutylene reaction with 1: 1.1 to 1: 2.5 mol ratio, simultaneously guarantee that under at least 160 ℃ temperature of reaction the concentration of diisobutylene keeps constant basically in entire reaction course, for some time is carried out in this reaction, so that 4,4 in the reaction mass (not comprising catalyzer) '-dioctyl diphenylamine is lower than 25wt%; And remove catalyzer and unreacted diisobutylene.This patent also discloses this product as the purposes of the anti-oxidant degraded of organic materials with stablizer.

U.S. Patent No. 6315925 discloses nonylated diphenylamine, particularly the mixture of dinonyl diphenylamines and by using the technical advantageous method of this mixture of small amount of acid Preparation of Catalyst.This mixture is easy to the organic products that oxidation, heat and/or photoinduction are degraded as additive in order to stablize.

U.S. Patent No. 6355839 discloses the method for preparing the alkylated diphenylamine antioxidant, this method is included in clay catalyst and exists down, use the polyisobutylene alkylate pentanoic, wherein the average molecular weight range of polyisobutene be 120-600 and wherein polyisobutene contain at least 25% methyl vinylidene isomer.

Aforementioned disclosure is incorporated herein by reference in full at this.

Summary of the invention

An object of the present invention is to provide with isobutylene oligomer and/or the alkylating novel diphenylamine compound of propylene oligomer.

Another purpose of the present invention provides the novel method that obtains this model mixture.

Another purpose of the present invention provides with the improving one's methods of alkene mixture alkylated diphenylamine, and this alkene mixture contains with respect to other fraction in the mixture, has the more fraction of hyperergy.

Still a further object of the present invention provides this mixture as the lubricant additive of effectively giving lubricating oil, fuel composition or rubber formulation antioxidant property.

Realize these and other objects by the present invention, wherein the present invention relates to prepare the method for lubricant additive, described lubricant additive is derived from diarylamine, the alkylated reaction of preferred pentanoic, described alkylated reaction is in the presence of the acid clay catalyzer, be enough to low under the temperature that prevents the remarkable inactivation of catalyzer, the fraction that will contain hyperergy, and the alkene mixture that demonstrates relatively low chemically reactive fraction adds in the diarylamine, finish up to interpolation, elevated temperature is to improve the alkylation rate of reactive lower fraction then.Represent alkylating pentanoic with following general formula:

R wherein ₁, R ₂, R ₃And R ₄Be independently selected from hydrogen, isobutylene oligomer and propylene oligomer, condition is R ₁, R ₂, R ₃And R ₄In at least one be not hydrogen.

This method produces that () mixture for example, pentanoic, this mixture demonstrates useful character and physicals with the oligopolymer of iso-butylene or the alkylating diarylamine of oligopolymer of propylene.

More particularly, the present invention relates to produce the method for the alkylated diphenylamine of following general formula:

R wherein ₁, R ₂, R ₃And R ₄Be independently selected from hydrogen, isobutylene oligomer and propylene oligomer, condition is R ₁, R ₂, R ₃And R ₄In at least one be not hydrogen, wherein this method is included in the existence of acid clay catalyzer down, be enough to low under the temperature that prevents the remarkable inactivation of catalyzer, the mixture of isobutylene oligomer or the mixture of propylene oligomer are joined in the pentanoic, wherein said mixture comprises the fraction of hyperergy, and reactive lower fraction, finish up to interpolation, elevated temperature is to improve the alkylation rate of reactive lower fraction then.

On the other hand, the present invention relates to the alkylated diphenylamine of following general formula:

R wherein ₁, R ₂, R ₃And R ₄Be independently selected from hydrogen, isobutylene oligomer and propylene oligomer, condition is R ₁, R ₂, R ₃And R ₄In at least one be not hydrogen, described alkylated diphenylamine prepares by following method, it comprises: in the presence of the acid clay catalyzer, be enough to low under the temperature that prevents the remarkable inactivation of catalyzer, the mixture of isobutylene oligomer or the mixture of propylene oligomer are joined in the pentanoic, and wherein said mixture comprises the fraction of hyperergy, and reactive lower fraction, finish up to interpolation, elevated temperature is to improve the alkylation rate of reactive lower fraction then.

More on the one hand, the present invention relates to a kind of composition, said composition comprises:

A) be selected from the organic products of lubricant, hydraulic fluid, metal working fluid, fuel and polymkeric substance; With

B) alkylated diphenylamine of the following general formula of stable quantity:

R wherein ₁, R ₂, R ₃And R ₄Be independently selected from hydrogen, isobutylene oligomer and propylene oligomer, condition is R ₁, R ₂, R ₃And R ₄In at least one be not hydrogen, described alkylated diphenylamine prepares by following method, it comprises: in the presence of the acid clay catalyzer, be enough to low under the temperature that prevents the remarkable inactivation of catalyzer, the mixture of isobutylene oligomer or the mixture of propylene oligomer are joined in the pentanoic, and wherein said mixture comprises the fraction of hyperergy, and reactive lower fraction, finish up to interpolation, elevated temperature is to improve the alkylation rate of reactive lower fraction then.

In preferred embodiments, R ₁Be isobutyl-, diisobutyl, triisobutyl, four isobutyl-s, five isobutyl-s, six isobutyl-s, seven isobutyl-s or other many isobutyl-s, or propylene oligomer, and R ₂, R ₃And R ₄Be independently selected from hydrogen, isobutyl-, diisobutyl, triisobutyl, four isobutyl-s, five isobutyl-s, six isobutyl-s, seven isobutyl-s or other many isobutyl-s, or propylene oligomer.

This compound can be used as antioxidant in the tire that is mixed, polyvalent alcohol, plastics, urethane, grease, machine oil, string rubber, cable, packing ring, sealing material and the rubber product in clothes and carpet industry.

The accompanying drawing summary

Fig. 1 is presented under 130 ℃ the temperature of reaction, and the DIB mol% of raw material deducts measured DIB mol% poor (Δ) chart as the function in reaction times.

Fig. 2 is presented under 145 ℃ the temperature of reaction, and the DIB mol% of raw material deducts measured DIB mol% poor (Δ) chart as the function in reaction times.

Fig. 3 is presented under 160 ℃ the temperature of reaction, and the DIB mol% of raw material deducts measured DIB mol% poor (Δ) chart as the function in reaction times.

The explanation of preferred embodiment

A kind of alkene mixture that uses in the invention process is the isobutylene oligomer with following distribution:

$\underset{x=2}{\overset{8}{\mathrm{\Σ}}}{C}_{4x}$

Be in or near mass transfer control speed (mass transfer controlled rate) under, in 130 ℃-160 ℃ temperature range, (simultaneously higher oligopolymer (n＞2) does not react diisobutylene for DIB, n=2) reaction.Because DIB is faster than the reaction of other oligopolymer, therefore, in reactor, with respect to the distribution of raw material, oligopolymer be distributed in C ₈The place occurs not enough.The distribution that this means oligopolymer in semicontinuous interpolation process can be used as catalyst activity in the reaction process as the measuring of the function of time, and this is because if by inactivation catalyst activity is sexually revised in the interpolation process, then as the function of time, and the C of this distribution ₈Component will increase.

Fig. 1,2 and 3 is presented at respectively under the temperature of reaction of 130 ℃, 145 ℃ and 160 ℃, and the DIB mol% of raw material deducts measured DIB mol% poor (Δ) chart as the function in reaction times.Under 130 ℃, this Δ keeps constant relatively and demonstrates uncorrelated with the reaction times.Under 145 ℃, this Δ is relevant with the reaction times really, and under the long reaction times, Δ descends.Under 160 ℃, observe and identical effect under 145 ℃, but degree is much bigger.Explanation to this behavior is a catalyst deactivation, and inactivation depends on temperature.Therefore, it is slower at 145 ℃ of following inactivations at 160 ℃ of following rapid deactivations, and under 130 ℃ inactivation not in fact.

For isobutylene example, in a word,

1) in the temperature range of being studied, C ₈Under the mass transfer control speed, react.

2) little (the nigh E of the temperature dependency of mass transfer velocity limited reactions _ActBe 5kcal/mol).

3) deactivation rate of catalyzer depends on temperature strongly.

Similarly, for the mixture of propylene oligomer:

1) with respect to the speed of other propylene oligomer with internal double bond, the alpha-olefin fraction in mixture is consumed with higher speed.

2) deactivation rate of catalyzer depends on temperature strongly.

For the distribution of these two kinds of oligopolymer, the fraction of all hyperergys is consumed, and simultaneously catalyzer keeps fresh, (at elevated temperatures) then, stays reactive lower fraction and reacts under the condition that the validity of catalyzer has significantly been reduced.

According to the present invention, arrange reaction conditions, so that in the interpolation process of alkene mixture, the inactivation of catalyzer keeps the speed of response of minimum and hyperergy fraction to be in or approaches mass transfer velocity.In case finish interpolation, can change reaction conditions (that is, elevated temperature), to increase the alkylation rate of other fraction.In such a way, people can obtain hyperergy fraction alkylating most of advantages fast, have prolonged the inactivation of catalyzer simultaneously, thereby have improved total speed of response.By this method, can in the short time period, obtain the very DPA of high conversion, reach＜1% residue.

In addition, known isobutylene oligomer experience " cracking ", that is, the process of oligomer chain is left in the one or more unit fracture in the iso-butylene.This takes place under acidic conditions at elevated temperatures.In any method of the oligopolymer alkylated diphenylamine of using iso-butylene, iso-butylene will produce regularly, and iso-butylene can participate in alkylation, produce tertiary butyl pentanoic and di-t-butyl pentanoic, and these two all has negative influence to product and/or performance characteristic.The method of the application of the invention can limit this two kinds of materials in final material.In addition, because isobutylene oligomer sluggish, " cracking " only is the remarkable factor under elevated temperature, therefore can pass through the fraction of consume reactive maximum at low temperatures, elevated temperature then, with rate of cleavage (and therefore having shortened the interior chain length of alkene that will react) and the alkylation rate that increases reactive lower fraction, thus the mean chain length of control alkylation material.

By aforesaid method, the molecular weight distribution of may command product also narrows to form described more favourable composition.Best pentanoic by 0.1-1% (DPA),＜10% tertiary butyl DPA,＜10% di-t-butyl DPA,＜single octyl group DPA of 10%,＞20% dodecyl DPA,＞15% hexadecyl DPA,＜10% eicosylene base DPA,＜7% tetracosa carbon thiazolinyl DPA,＜mixture that 4% two vaccenic acid base DPA and many isobutyl-s DPA of＜2% form.In addition, being not more than 27% complete reaction mixture can be by C ₈Or the alkylation of even lower level material constitute and be not more than 15% complete reaction mixture can be by C ₂₄Or the alkylation of more senior material constitutes.In case finish stripping, this mixture also can contain about 5% unreacted alkene at most.

Except pentanoic, other arylamine also can carry out alkylation by the inventive method.These other arylamine comprises, for example, and N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamines, p, p '-phenylenediamine, thiodiphenylamine, phenoxazine, mutual-amido two polyaniline, to methylamino pentanoic and p-isopropyl aminodiphenylamine.

Therefore, the invention provides alkylating pentanoic, it is a kind of good antioxidant by following method preparation: under suitable alkylation reaction condition, in the presence of the acid clay alkylation catalyst, with iso-butylene or propylene oligomer alkylated diphenylamine.

In general, the number-average molecular weight of isobutylene oligomer is about 120-about 600, preferably in about 400 scopes of about 150-, more preferably in about 280 scopes of about 160-, be at least about 25% with the methyl vinylidene content, preferably in about 95% scope of about 25%-, more preferably in about 95% scope of about 40%-and even more preferably in about 90% scope of about 60%-.Diisobutylene (C ₈) can scope be that the mark consumption of 0%-about 50% and preferably about 10%-about 50% is present in the polyisobutene.

Disclose in U.S. Patent No. 3452056 and used clay as catalyzer in the alkylation of pentanoic, this patent has been described and has been used clay as catalyzer alpha-methyl styrene and relevant olefin alkylation diphenylamines.In U.S. Patent No. 2943112 and other document, clay is described to have several advantages, comprises, for example: it provides more shallow painted product (1), and after reaction, it can be easily by removing by filter (2), (3) in alkylate, it provides the yellow than low degree.As catalyzer, clay and other Lewis acid are as AlCl ₃Or BF ₃, usually by instruction interchangeable (referring to, United States Patent(USP) Nos. 3452056 and 5672752).Recently, United States Patent(USP) Nos. 5672752,5750787 and 6204412 has been identified some commercially available clay catalyst, comprising the Filtrol available from Engelhard ^TMAnd Retrol ^TMFulcat available from Laporte Industries ^TM14, Fulmont ^TM700c, Fulmont ^TM237 and Fulcat ^TM22B; With Katalysator available from SudChemi ^TMK10.These clays can comprise the clay of acid activation or acid leach.This clay catalyst can contain some water that former state is accepted.Before using, remove to anhydrate and cause more shallow painted reaction product.Therefore, the hope use has the clay of low water content or by heating clay with nitrogen purging or with coupling vacuum stripping, anhydrates to remove.Preferred acid activatory clay; Yet,, can use Lewis acid, as AlCl if special situation is licensed ₃Or BF ₃And the BF of diethyl ether, phenol ₃Complex compound is comprising the mixture of itself and clay.

The invention still further relates to the composition that contains stablizer, it comprise the organic products that is easy to oxidation, heat and/or photoinduction degraded and as above the mixture of definition and alkylated diphenylamine prepared according to the methods of the invention as stablizer.

By spendable lubricant under 200 ℃ and above temperature with based on operating fluid (operationalfluid) or the synthetic lubricant or the operating fluid of mineral oil, carboxylates derivatives for example, form the special organic products of a class that non-required oxidative degradation takes place easily, wherein for above-mentioned product, mixture of the present invention is valuable stablizer.

Can use mixture of the present invention with the concentration of the about 10.0wt% of about 0.05-based on treating stable material.Preferred concentration is 0.05-5.0wt%, particularly 0.1-2.5wt%.

Improved in such a way mineral and ucon oil, lubricating grease, hydraulic fluid and elastomer display go out excellent antioxidant property, and the antioxidant property of this excellence becomes apparent by the remarkable decline of the catabiosis that the described part that is protected demonstrates.Above-described mixture particularly advantageous in lubricating oil, in lubricating oil, they demonstrate excellent anti-oxidant and anticorrosive effect, and do not form acid or sludge.

The example of ucon oil comprises based on following lubricant: the diester of diprotic acid and monohydroxy-alcohol, for example, dioctyl sebacate or dinonyl adipate; Three esters of the mixture of TriMethylolPropane(TMP) and monoprotic acid or this acid, for example, three pelargonates of TriMethylolPropane(TMP) or three octanoates or its mixture; Four esters of the mixture of tetramethylolmethane and monoprotic acid or this acid, for example, tetramethylolmethane four octanoates; Or the complex ester (complexester) of monoprotic acid or diprotic acid and polyvalent alcohol, for example, TriMethylolPropane(TMP) and complex ester sad and sebacic acid or its mixture.

Other synthetic lubricant is appreciated by those skilled in the art, and for example is described in " Schmiermittel Taschenbuch " (Huthig-Verlag, Heidelberg, 1974).Specially suitable for example is poly-alpha-olefin, ester-based lubricant, phosphoric acid ester, dibasic alcohol, polyglycol and polyalkylene glycol.

Suitable elastomerics is appreciated by those skilled in the art.Specially suitable is natural and synthetic rubber, for example, the polymkeric substance of divinyl and with multipolymer and the isoprene or the chloroprene polymer of vinylbenzene or vinyl cyanide.

Can form the another kind of polymkeric substance that is protected by polycondensation; by adding above-described mixture; under the macromole finished product state of condensation and under low-molecular-weight parent material state, described polymkeric substance all can be protected, to avoid oxidation and photoinduced degraded.This base polymer can be by adding dinonyldiphenylamine to for example stable as making it in its basic polyvalent alcohol particularly including urethane.

Also mixture of the present invention can be joined in the natural and synthesis of organic substance matter, described organic substance is pure monomeric compound or its mixture, for example, mineral oil, animal or plant oil, wax and fat or oil, wax and based on the fat of synthetic ester, for example, phthalic ester, adipic acid ester, phosphoric acid ester or trimellitate and have the synthetic ester of any required weight ratio and the blend of mineral oil for example use as spinning (spinning) preparation and aqueous emulsion thereof.

Mixture of the present invention can be joined in natural or the elastomeric natural and synthetic emulsion, for example in the latex of natural rubber latex or carboxylated styrene/butadiene copolymers.

Be derived from additive of the present invention can be used as the commercially available antioxidant that uses at present in lubricant formulations substitute wholly or in part.Additive of the present invention can be used in combination with other additive of typically finding in lubricating oil, and in fact this combination can provide synergistic effect to lubricating oil, improving desired properties, as improved deposition control, wear-resisting, friction, anti-oxidant, low temperature and similar performance.The typical additive of finding in machine oil and fuel is dispersion agent, purification agent, rust-preventive agent, antioxidant, anti-wear agent, defoamer, friction modifiers, packing ring (seal) swelling agent, emulsion splitter, viscosity index (VI) improving agent and pour point depressor.Referring to, for example U.S. Patent No. 5498809 is about the description of useful lubricating oil composition additive, and its disclosure is hereby incorporated by in full.

The example of dispersion agent comprises polyisobutenyl succinimide, polyisobutylene succinic acid ester, Mannich Base ashless dispersants and analogue.The example of purification agent comprises metal and ashless alkyl phenate, metal and ashless alkyl monosulfide phenates, metal and ashless alkylsulfonate, metal and ashless alkylsalicylate, metal and ashless salicin derivatives and analogue.

The example of antioxidant comprise alkylated diphenylamine, N-alkylated phenylenediamines, phenyl-a-naphthylamine, alkylation phenyl-alpha-naphthylamine, dimethyl quinoline, trimethyldihydroquinoline and by its deutero-oligomeric composition, hindered phenol, alkylation quinhydrones, hydroxylation sulfo-phenyl ether, alkylidene bisphenols, thiopropionate, metal dithionite for carbaminate, 1,3,4-dimercaptothiodiazole and derivative, oil-soluble copper compounds and analogue.Following exemplifying of especially this additive, and commercially available in Crompton Corporation:Naugalube ^438, Naugalube 438L, Naugalube 640, Naugalube 635, Naugalube 680, Naugalube AMS, Naugalube APAN, Naugard PANA, NaugalubeTMQ, Naugalube 531, Naugalube 431, Naugard ^BHT, Naugalube 403 and Naugalube 420.

The example of the anti-wear additive that can be used in combination with additive of the present invention comprises organic boric acid ester, organophosphite, organophosphate, sulfur-containing organic compound, olefine sulfide, sulfurized fatty acid derivative (ester), chlorinated paraffin, zinc dialkyl dithiophosphate, diaryl zinc dithiophosphate, phosphoric acid sulfurized hydrocarbon (phosphosulfurized hydrocarbon) and analogue.Following exemplifying of especially this additive, and commercially available in The LubrizolCorporation:Lubrizol 677A, Lubrizol 1095, Lubrizol 1097, Lubrizol 1360, Lubrizol 1395, Lubrizol 5139 and Lubrizol 5604.

The example of friction modifiers comprises the molybdenum compound and the analogue of fatty acid ester and acid amides, organic molybdenum, molybdenum dialkyldithiocarbamacompositions, molybdenum dialkyl-dithiophosphate, molybdenumdisulphide, dialkyldithiocarbamacompositions three molybdenum nanoclusters, no sulphur.Following exemplifying of especially this additive, and commercially available in R.T.Vanderbilt Company, Inc.:Molyvan A, Molyvan L, Molyvan 807, Molyvan 856B, Molyvan 822, Molyvan 855.Following also exemplifying of especially this additive, and commercially available in Asahi Denka KogyoK.K.:SAKURA-LUBE 100, SAKURA-LUBE 165, SAKURA-LUBE 300, SAKURA-LUBE 310G, SAKURA-LUBE 321, SAKURA-LUBE 474, SAKURA-LUBE600, SAKURA-LUBE 700.Following also exemplifying of especially this additive, and commercially available in Akzo Nobel Chemicals GmbH:Ketjen-Ox 77M, Ketjen-Ox 77TS.

The example of defoamer is polysiloxane and analogue.The example of rust-preventive agent is polyoxyalkylene polylol, benzotriazole derivatives and analogue.The example of VI improving agent comprises olefin copolymer and dispersant olefin copolymers and analogue.The example of pour point depressor is polymethacrylate and analogue.

As mentioned above, suitable wear compounds comprises dialkyl dithiophosphate.Preferably, alkyl contains on average at least 3 carbon atoms.Particularly advantageous is the metal-salt of at least a dialkyl phosphorodithioic acid, and wherein alkyl contains on average at least 3 carbon atoms.

Lubricant compositions

When composition contains these additives, typically they are blended in the base oil, its consumption makes additive wherein that its normal attach feature can effectively be provided.Listed the representative significant quantity of these additives in the following table.

Additive	Preferred weight %	More preferably weight %
			V.I. improving agent	1-12	1-4
Sanitas	0.01-3	0.01-1.5
			Oxidation retarder	0.01-5	0.01-1.5
Dispersion agent	0.1-10	0.1-5
			The lubricating oil improving agent that flows	0.01-2	0.01-1.5
Purification agent/rust-preventive agent	0.01-6	0.01-3
			Pour point depressor	0.01-1.5	0.01-0.5
Defoamer	0.001-0.1	0.001-0.01
			Anti-wear agent	0.001-5	0.001-1.5
The packing ring swelling agent	0.1-8	0.1-4
			Friction modifiers	0.01-3	0.01-1.5
Lubricating base oil	Surplus	Surplus

When using other additive, may it is desirable to, but it is not necessary, preparation contains the strong solution of subject additives of the present invention and one or more other additives or the additive concentrate feed of dispersion liquid, and (this concentrate feed is when the formation additive agent mixture, be called as additive-package herein), so several additives can join in the base oil simultaneously to form lubricating oil composition.Can promote the dissolving of additive concentrate feed in lubricating oil by solvent with by the mixing (but this is optional) of following mild heat.Typically prepare concentrate feed or additive-package to contain an amount of additive, when combining with the base lubricant of predetermined amount, in final preparation, provide required concentration with convenient additive-package.Therefore, subject additives of the present invention can be joined in a small amount of base oil or other the compatible solvent with other required additive, contain total amount with suitable ratio formation and typically be the about 90wt% of about 2.5-, the preferred about 75wt% of about 15-and more preferably from about additive activeconstituents and the surplus of the about 60wt% of 25-are the additive-package of base oil.It is base oil that final preparation can typically use the additive-package of about 1-20wt% and surplus.

The all wt percentage ratio (except as otherwise noted) of Biao Daing is based on the content of activeconstituents in the additive (AI) herein, and/or based on the gross weight of any additives bag or preparation, the gross weight of described additive-package or preparation is the weight sum that the AI weight of each additive adds whole oil or thinner.

In general, composition of the present invention contains the additive of concentration range for the about 30wt% of about 0.05-.Be preferably based on the gross weight of oil compositions, the concentration range of additive is the about 10wt% of about 0.1-.Preferred concentration range is the about 5wt% of about 0.2-.In the carrier or diluent oil of lubricating oil viscosity, the oily concentrate feed of additive can contain the additive reaction product of the about 75wt% of 1-that has an appointment.

In general, additive of the present invention can be used in the various lube base raw materials.The lube base raw material is to be the about 200cSt of about 2-, the more preferably from about about 150cSt of 3-and the most preferably from about any natural or synthetic lube base raw material fraction of the about 100cSt of 3-100 ℃ of following kinematic viscosity.The lube base raw material can be derived from natural lubricating oil, ucon oil or its mixture.The proper lubrication oil base stocks is drawn together the basic material that the isomerization by synthetic wax and wax obtains, and the basic material of the hydrocracking of producing by aromatics in hydrocracking (rather than solvent extraction) crude oil and polar compound.Natural lubricating oil comprises animal oil (as, lard), vegetables oil (for example, Tower rape oil, Viscotrol C, sunflower oil), oil, mineral oil and is derived from coal or the oil of shale.

Synthetic oil comprises the hydrocarbon-type oil that hydrocarbon-type oil and halogen replace, as the alkene of polymerization and copolymerization, by the preparation of fischer-tropsch technology gas-liquid (gas-to-liquid), alkylbenzene, polyphenyl, alkylation phenyl ether, alkylation diphenyl sulfide with and derivative, analogue, homologue etc.Ucon oil also comprises alkylene oxide polymer, interpretation, multipolymer and derivative thereof, and wherein terminal hydroxy group is by modifications such as esterification, etherificates.Another kind of suitable ucon oil comprises the ester of di-carboxylic acid and various alcohol.The ester that can be used as synthetic oil also comprises by C ₅-C ₁₂Those that monocarboxylic acid and polyvalent alcohol and polyol ethers are made.Other ester that can be used as synthetic oil comprises those that make by alpha-olefin with by the multipolymer of the di-carboxylic acid of the pure esterification of short or medium chain.Following exemplifying of especially this additive, and commercially available in Akzo Nobel Chemicals SpA:Ketjenlubes 115,135,165,1300,2300,2700,305,445,502,522 and 6300.

Silicon-based oil, as many alkyl-, polyaryl-, many alkoxyl groups-or the silicone oil and the silicic acid ester oil of many aryloxy, comprise another kind of useful ucon oil.Other ucon oil comprises the liquid ester of phosphoric acid, tetrahydrofuran (THF), poly-alpha olefins and the analogue of polymkeric substance.

Lubricating oil can be derived from not refining, refining, purified oil or its mixture again.Can under the situation that is not further purified or handles, directly obtain unrefined oil by natural origin or synthetic source (for example, coal, shale or tar and pitch).The example of unrefined oil comprises the shale oil that directly obtained by retorting operation, the petroleum oil that is directly obtained by distillation or the ester oil that is directly obtained by esterification technique, and each in these can be used under the situation that not have further processing then.Refining oil is similar to not refining oil, and different is that refining oil is handled to improve one or more performances in a step or multistep purification step.Suitable purification technique comprises distillation, hydrogen treatment, dewaxing, solvent extraction, acid or alkali extraction, filtration, diafiltration etc., and all these purification techniques all are known in those skilled in the art.By adopting and obtaining the similar art breading refining oil of the employed technology of refining oil, obtain refining oil again.These again refining oil also be called as recovered oil or reprocessed oils, and usually the technology of the degradation production by removing useless additive and oil is handled in addition.

Also can use or use the lube base raw material of the hydrogenation isomerization that is derived from wax separately in conjunction with aforementioned natural and/or synthetic basic material.By on hydrogenation isomerization catalyst, hydrogenation isomerization natural or synthetic wax or its mixture are produced the isomery oil of this wax.The slack wax that natural wax reclaims by the solvent dewaxing of mineral oil typically; Synthetic wax typically is the wax of producing by fischer-tropsch process.The gained isomerization product is typically carried out solvent dewaxing and classification, have the various fractions of particular viscosity scope with recovery.The feature of the isomer of wax also is to have very high viscosity index, and usually VI be at least 130, and preferably at least 135 or higher and after dewaxing, pour point is-20 ℃ or lower of pacts.

Additive of the present invention can be particularly useful as the component in many different oils compositions.This additive can be included in the various oil with lubricant viscosity, comprising natural and ucon oil and composition thereof.This additive can be included in the oil engine of spark ignition and ignition with in the crankcase oil.Said composition also can be used in gas engine lubricant, turbine lubricants, spontaneously transporting fluids, gear lubricant, compressor lubricant, metal working lubricant, hydraulic fluid and other lubricating oil and the fat or oil composition.This additive also can use in motor fuel composite and rubber formulation.

According to following embodiment, it is more apparent that advantage of the present invention and key character will become.

Embodiment

Embodiment 1

Heating 150g (0.89mol) pentanoic to 60 ℃.To wherein adding 45g Filtrol 20x, and heat this mixture to 130 ℃.In 4.167 hours, add PIB distillate (382.5g) then.In case added all reactants, then reaction mass kept 18 hours under this temperature.Remove catalyzer, and under vacuum, strip residual parent material.

Embodiment 2

Heating 150g (0.89mol) pentanoic to 60 ℃.To wherein adding 45g Filtrol 20x, and heat this mixture to 145 ℃.In 5.917 hours, add PIB distillate (382.5g) then.In case added all reactants, then reaction mass kept 16 hours under this temperature.Remove catalyzer, and under vacuum, strip residual parent material.

Embodiment 3

Heating 150g (0.89mol) pentanoic to 60 ℃.To wherein adding 45g Filtrol 20x, and heat this mixture to 160 ℃.In 4.217 hours, add PIB distillate (382.5g) then.In case added all reactants, then reaction mass kept 4 hours under this temperature.Remove catalyzer, and under vacuum, strip residual parent material.

Embodiment 4

Heating 150g (0.89mol) pentanoic to 60 ℃.To wherein adding 45g Filtrol 20x, and heat this mixture to 130 ℃.Add PIB distillate (382.5g) under the speed of temperature of reaction being enough to keep then.In case added all reactants, elevated temperature to 150 ℃ also kept 12 hours.Remove catalyzer, and under vacuum, strip residual parent material.

Oxidation test

The thermal test of pressure reduction scanning amount

In pressure reduction scanning calorimetric (PDSC) test, measure the antioxidant property of reaction product.According to the operation of general introduction, use Mettler Toledo DSC27HP tester to test.The antioxidant that this experimental measurement is measured in oxygen under pressure is at the intravital relative oxidation induction time of lubrication flow (OIT).

Sample to be tested is blended into the standard that does not contain antioxidant with the amount of 0.4wt% prepares (referring to table 1) in the machine oil entirely.Add extra 0.1wt%Solvent Neutral 150 base oils with the 50ppm iron naphthenate then.Then these and the basic blend sample that contains 0.5wt% SolventNeutral 150 base oils and 50ppm iron naphthenate are compared.Table 2 shows test condition.In table 3, the numerical value of test-results (OIT, minute) increase along with the increase of validity.

Table 1 is used for the basic blend of PDSC test
		Component	wt％
Solvent Neutral 150	83.85
		Zinc dialkyl dithiophosphate	1.01
Succinimide dispersants	7.58
		Overbased calcium sulfonate detergent	1.31
The neutral calcium sulfonate purification agent	0.5
		Antioxidant	0.0
Rust-preventive agent	0.1
		Pour point depressor	0.1
OCP VI improving agent	5.55

Table 2 PDSC condition
		Condition	Be provided with
Temperature	200℃
		Gas	Oxygen
Flow velocity	100ml/min
		Pressure	500psi
Sample size	1-5mg
		Ware (open/airtight)	Open

Table 3 PDSC result
		Compound	OIT
The basis blend	5.45
		Embodiment 1	17.03
Embodiment 2	18.74
		Embodiment 3	18.48
Embodiment 4	18.21

Table 4 is 40 ℃ of viscosity of measuring by ASTM D445 down
		Compound	Viscosity
Embodiment 1	1082
		Embodiment 2	1300
Embodiment 3	1244
		Embodiment 4	1050

In view of can under the principle situation that does not depart from as basis of the present invention, making many variations and change, therefore should will offer protection scope of the present invention to understand with reference to claims.

Claims (12)

1. method of producing the alkylated diphenylamine of following general formula:

R wherein ₁, R ₂, R ₃And R ₄Be independently selected from hydrogen, isobutylene oligomer and propylene oligomer, condition is R ₁, R ₂, R ₃And R ₄In at least one be not hydrogen, wherein this method is included in the existence of acid clay catalyzer down, be enough to low under the temperature that prevents the remarkable inactivation of catalyzer, the mixture of isobutylene oligomer or the mixture of propylene oligomer are joined in the pentanoic, wherein said mixture comprises the fraction of hyperergy, and reactive lower fraction, finish up to interpolation, elevated temperature is to improve the alkylation rate of reactive lower fraction then, obtain product, described product comprises the pentanoic of 0.1-1%,＜10% tertiary butyl pentanoic,＜10% di-t-butyl pentanoic, single octyl diphenylamine of＜10%,＞20% dodecyl diphenylamine,＞15% hexadecyl pentanoic,＜10% eicosylene base pentanoic,＜7% tetracosa carbon thiazolinyl pentanoic,＜4% two vaccenic acid base pentanoic and many isobutyl-s pentanoic of＜2%.

2. the process of claim 1 wherein be not more than 27% complete reaction mixture can be by C ₈Or the alkylation of even lower level material constitute and be not more than 15% complete reaction mixture can be by C ₂₄Or the alkylation of more senior material constitutes.。

3. the process of claim 1 wherein that the number-average molecular weight of isobutylene oligomer is at least about 25% for about 120-about 600 and methyl vinylidene content.

4. the alkylated diphenylamine of following general formula:

R wherein ₁, R ₂, R ₃And R ₄Be independently selected from hydrogen, isobutylene oligomer and propylene oligomer, condition is R ₁, R ₂, R ₃And R ₄In at least one be not hydrogen, wherein said alkylated diphenylamine prepares by following method, it comprises: in the presence of the acid clay catalyzer, be enough to low under the temperature that prevents the remarkable inactivation of catalyzer, the mixture of isobutylene oligomer or the mixture of propylene oligomer are joined in the pentanoic, wherein said mixture comprises the fraction of hyperergy, and reactive lower fraction, finish up to interpolation, elevated temperature is to improve the alkylation rate of reactive lower fraction then, obtain product, described product comprises the pentanoic of 0.1-1%,＜10% tertiary butyl pentanoic,＜10% di-t-butyl pentanoic, single octyl diphenylamine of＜10%,＞20% dodecyl diphenylamine,＞15% hexadecyl pentanoic,＜10% eicosylene base pentanoic,＜7% tetracosa carbon thiazolinyl pentanoic,＜4% two vaccenic acid base pentanoic and many isobutyl-s pentanoic of＜2%.

5. the alkylated diphenylamine of claim 4, wherein being not more than 27% complete reaction mixture can be by C ₈Or the alkylation of even lower level material constitute and be not more than 15% complete reaction mixture can be by C ₂₄Or the alkylation of more senior material constitutes.

6. the alkylated diphenylamine of claim 4, wherein the number-average molecular weight of isobutylene oligomer is at least about 25% for about 120-about 600 and methyl vinylidene content.

7. composition, said composition comprises:

A) be selected from the organic products of lubricant, hydraulic fluid, metal working fluid, fuel and polymkeric substance; With

B) alkylated diphenylamine of the following general formula of stable quantity:

R wherein ₁, R ₂, R ₃And R ₄Be independently selected from hydrogen, isobutylene oligomer and propylene oligomer, condition is R ₁, R ₂, R ₃And R ₄In at least one be not hydrogen, wherein said alkylated diphenylamine prepares by following method, it comprises: in the presence of the acid clay catalyzer, be enough to low under the temperature that prevents the remarkable inactivation of catalyzer, the mixture of isobutylene oligomer or the mixture of propylene oligomer are joined in the pentanoic, wherein said mixture comprises the fraction of hyperergy, and reactive lower fraction, finish up to interpolation, elevated temperature is to improve the alkylation rate of reactive lower fraction then, obtain product, described product comprises the pentanoic of 0.1-1%,＜10% tertiary butyl pentanoic,＜10% di-t-butyl pentanoic, single octyl diphenylamine of＜10%,＞20% dodecyl diphenylamine,＞15% hexadecyl pentanoic,＜10% eicosylene base pentanoic,＜7% tetracosa carbon thiazolinyl pentanoic,＜4% two vaccenic acid base pentanoic and many isobutyl-s pentanoic of＜2%.

8. the composition of claim 7, wherein being not more than 27% complete reaction mixture can be by C ₈Or the alkylation of even lower level material constitute and be not more than 15% complete reaction mixture can be by C ₂₄Or the alkylation of more senior material constitutes.

9. the composition of claim 7, the number-average molecular weight that wherein joins the isobutylene oligomer in the pentanoic is at least about 25% for about 120-about 600 and methyl vinylidene content.

10. the composition of claim 7, wherein based on treating stable material, alkylated diphenylamine exists with the concentration of the about 10.0wt% of about 0.05-.

11. the composition of claim 7, wherein organic products is a lubricating oil.

12. the composition of claim 7, wherein organic products is an elastomerics.

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