CN1241195A - Functionalized polymers - Google Patents

Functionalized polymers Download PDF

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CN1241195A
CN1241195A CN98801424A CN98801424A CN1241195A CN 1241195 A CN1241195 A CN 1241195A CN 98801424 A CN98801424 A CN 98801424A CN 98801424 A CN98801424 A CN 98801424A CN 1241195 A CN1241195 A CN 1241195A
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aromatic nucleus
group
polymkeric substance
systems
side chain
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B·伊凡
F·德乔
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INFENUM BV
Infineum Holdings BV
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Abstract

The invention discloses a process for functionalizing polymers prepared by carbocationic polymerization wherein a living carbocationic polymerization system is reacted with one or more aromatic ring systems, and the use of substituted or unsubstituted reaction products of said process in lubricating oil or fuel compositions and additive concentrates, for example as dispersant, detergent or antioxidant additives or VI improvers.

Description

Functionalized polymeric
The present invention relates to a kind of functionalized novel method of the polymkeric substance for preparing by the carbocation catalyzed polymerization, and relate to novel functionalized polymeric, as the telechelic prepolymer.
The polymkeric substance that has functional group can be used as slip additive, compatilizer, emulsifying agent or as the raw material of producing tackiness agent, properties-correcting agent, coating, sealing material etc.Therefore, people have keen interest to functionalized polymeric always.
The carbocation catalyzed polymerization is a kind of in the preparation functionalized polymeric currently known methods.For example, WO-A-94/13706 has disclosed a kind of direct synthetic method of passing through the active cation catalyzed polymerization of the functionalized novel polymerizable material of nitrogen-containing functional group.Wherein, with the mode of basic synchronization (available from, with a step Friedel-Crafts reaction) polymerization and functionalization take place.At the book of teaching " by the structural polymer of carbocation macromole engineering: theory and practice " [" DesignedPolymers by Carbocationic Macromolecular Engineering:Theoryand Practice " (Hanser Publishers, 1991)] in the II.5.2. part, author J.P.Kennedy and B.Ivan provide many and not only had the auxilliary example that adds end group in polyolefine but also in poly-(alkyl vinyl ether), but normally prepare with two-step approach.
It should be understood that with what a step carbocation catalyst polymerization made to have novel end group and have the polymkeric substance of potential further reaction, will be to wish especially.
Therefore, had found that a kind of functionizing method of the polymkeric substance for preparing by the carbocation catalyzed polymerization, wherein, activated carbon cationic polymerization system and the reaction of one or more aromatic nucleus system.
When one or more aromatic nucleus systems are selected from Wuyuan, six atoms or seven atom heterocycles, this method will be specially suitable.Described heterocycle will contain one or more N of being selected from, O, and the heteroatoms of P and S, and usually provide that to react be the required polyelectrons environment of Friedel-Crafts reaction.Preferably, one or more aromatic nucleus systems are selected from six-π-electronics member ring systems.The example of special preferred fragrance member ring systems comprises: pyrroles, furans, thiophene, oxazole, isothiazole, 1,3,4-thiadiazoles and pyrazoles.These aromatic nucleus systems can partly be substituted, and the substituting group that is provided neither can spatially hinder the remaining reactive site of aromatic nucleus system, also can not make the passivation of aromatic nucleus system.For example, described substituting group can be selected from: amino, hydroxyl, alkoxyl group, aminocarboxyl, alkyl or aryl group, or halogen atom.The substituting group of at first mentioning is strong active group.Described substituting group may be sizable, and for example, the aromatic nucleus system rises under the situation of action of coupling agents therein, and this its molecular weight of first substituting group is equivalent to half of (on average) functionalized polymeric molecular weight.The example of the aromatic nucleus system of suitable replacement comprises: for example 3, and 3-dimethyl-3H-pyrazoles and 2,2-dithienyl.
One or more aromatic nucleus systems also can be selected from: (benzo-) the condensed ring system, as naphthalene, quinoline, quinoxaline, indoles, cumarone, thionaphthene, pteridine, purine, indolizine etc.In addition, also available above-mentioned identical substituting group carries out part to these one or more aromatic nucleus systems and replaces.
Preferably, one or more aromatic nucleus systems are selected from: the kind of pyrroles, furans and thiophene and their replacement.The polymkeric substance that so makes also can be known and very chemistry is further functionalized widely by pyrroles, furans and confused noise structure.Use the additional advantage of thiophene or substituted thiophene to be: functionalized polymeric inherent antioxidant properties.
Be to be noted that the definition of employed reactive polymer in whole specification sheets, consistent with the definition in the book of teaching of WO-A-94/13706 and above-mentioned Kennedy and Ivan.Therefore, activated carbon cationic polymerization system comprises: based on the ideal activity polymerization that does not wherein have chain transfer and terminated positively charged ion initiation with wherein there is an accurate living polymerization effect that the speed of the chain transfer that can reverse rapidly and/or termination and these processes will be faster than rate of rise.In other words, in system, the speed of irreversible chain transfer and/or termination is zero or almost nil.
As in the described book of teaching, being discussed, (activity) carbocation catalytic polymer is the polymkeric substance that promptly forms by control simple function or multifunctional initiator by the control initiation, whereby, polymer chain will be at one end in one direction or a plurality of directions that begin from the center increase.
Suitable activated carbon cationic polymerization system is: for example, and tertiary alkyl ester/BCl 3Withered ester/the TiCl of acetate 42,2 '-bipyridyl/TiCl 4CH 3SO 3H/SnCl 4+ n-Bu 4NCl; HI/I 2HI/ZnX 2Or SnX 2(X=Cl, Br); HI/ZnI 2Or CH 3COClO 4, for example use iso-butylene respectively as monomer; Iso-butylene/2,4-dimethyl-1,3-pentadiene; Vinylbenzene; Right-the ethenylphenyl glyceryl ether; IVE; Methylvinylether/to methoxy styrene; Or 2-methyl dihydrofuran (for more comprehensively tabulation, can be) referring to the Table IV in the above-mentioned book 43-55 page or leaf of teaching.In addition, also can use the nitrogenous compound that in WO-A-94/13706, is used as initiator, as 2-azido--isopropyl benzene or two (2-azido--sec.-propyl) benzene and diethyl aluminum chloride, TiCl 4Or BCl 3Mixture.
Although can use insoluble catalyzer, preferably use homogeneous catalyst.In polymerization process, use solvent usually.Its freezing point of suitable solvent is lower than preferred polymerization temperature.The solvent of illustrative includes but are not limited to:: C 2-C 10Alkanes, alkene class, alkyl halide and alkenyl halide, tetracol phenixin, dithiocarbonic anhydride, nitroethane, liquid carbon dioxide and methyl cyclohexanol.In addition, can also use mixed solvent.Preferred solvent is the lower boiling alkyl halide: methyl chloride, chloric ethane, chloro-propane, n-propylcarbinyl chloride and 1,2-ethylene dichloride; And neopentane, hexane, the sherwood oil of pentane and purification.
Can use the polymerisable monomer of any cationization, the alpha-olefin that comprises straight chain and side chain, isoolefine, aliphatic monoolefine, cycloaliphatic compounds, styrene derivatives, indenes and derivative thereof, and in article " cationic polymerization of alkene: critical component (ACritical Inventory) " the 39-53 page or leaf (Wiley, 1975) of Kennedy determined other monoolefine and the polymerisable monomer of heterocycle cationization.Also can use vinyl ether in addition.
Isoolefine or its mixture according to 4-20 carbon atom can make valuable especially polymkeric substance.The example of described unsaturated hydrocarbons is including, but not limited to iso-butylene, 2-methyl-butylene, 3-methyl-1-butene, 4-methyl-1-pentene, and beta-pinene.The polymerisable monomer of other operable cationization comprises: heterocyclic monomer ， such as oxazoline and other known heterocyclic monomer that adds polar covalent bond.If desired, can be used as raw material the polymerisable monomeric mixture of cationization is used for polymeric area.Therefore,, can make multipolymer, terpolymer and high-grade interpolymer more by using two kinds, three kinds or more kinds of above-mentioned monomer.Adding to the preferred raw material of polymeric area comprises: pure iso-butylene and the C that comprises iso-butylene 4The mixing raw material of hydrocarbon is as the C that is obtained by the heating of for example petroleum naphtha or catalytic pyrolysis operation 4Cut.In the weight of charging, suitable iso-butylene raw material will comprise at least 10% usually, at the most the iso-butylene of 100% weight.Industrial be important, usually be suitable for the C that makes raw material 4Cut comprises: the 1-butylene of 10-40%, and the 2-butylene of 10-40%, the Trimethylmethane of 40-60%, the normal butane of 4-10%, and about at the most 0.5% divinyl, all percentage number averages are in feed weight.In addition, the raw material that comprises iso-butylene can also comprise a small amount of other non-C 4The polymerizable alkylene hydrocarbon monomer for example is less than 25% usually, preferably is less than 10%, and the best is less than 5%, as propadiene, and propylene and C 5Alkene.The term of Shi Yonging " polyisobutene " not only comprises the homopolymer of iso-butylene in the present invention, and comprises iso-butylene and conventional C 4Other C of one or more of cut 4Polymerisable monomer and comprise 3-6 usually, preferably comprise the non-C of 3-5 carbon atom 4The monomeric multipolymer of olefinic unsaturated olefin, precondition are that in polymkeric substance number-average molecular weight (Mn), described multipolymer comprises: usually at least 50%, preferably at least 65%, and the iso-butylene unit of at least 80% weight most preferably.Under certain conditions of the present invention, the selective polymerisation performance of iso-butylene has guaranteed the iso-butylene of above-mentioned minimized content.
Preferably, polymerisation medium does not have toxicity substantially to catalyzer.For example, can by use molecular sieve to alkene charging handle, and carry out alkali cleaning to remove for example mercaptan, water and diene (if desired).
Polyreaction can be carried out off and on, or carries out in the mode of (partly) operate continuously, and the successive materials flow of wherein will preparing burden is delivered in the reactor, and takes out the overflow of polymer slurries or solution, so that therefrom reclaim polymkeric substance.Consider that from the angle of operation preferred reactive mode is to use the operate continuously mode of the reactor of continuous flow stirring, wherein charging is introduced continuously and also from reactor, taken out product in the reactor continuously with controllable manner.Yet,, preferably use periodical operation in the occasion of the product of producing more explication (narrow molecular weight distributions).
The catalyst consumption of Shi Yonging can change in the methods of the invention, so that reach the number of targets average molecular weight of polymkeric substance.Change catalyst consumption and can also make isomerization become minimum, or reduce undesirable isomerization.Initiator concentration is low more in reacting phase, and the molecular weight of polymkeric substance is just high more, and vice versa.When plan is used as dispersion agent with polymkeric substance in lubricating oil, being controlled at polymericular weight in the determined scope of selected subject polymer molecular weight will be particularly important.Catalyst consumption also will influence the yield of the transformation efficiency and the polymkeric substance of olefinic monomer, and higher catalyst levels will obtain higher transformation efficiency and yield usually.Catalyst consumption is as the criterion to be enough to making reaction become " activity " cationoid polymerisation.
For inducing linearity or chain polymerization rather than forming ring or side chain, polyreaction is carried out in liquid phase.If when using under envrionment conditions the charging as gas phase, preferably, control reaction pressure and/or charging is dissolved in inert solvent or the liquid diluent is so that make charging keep liquid phase.As C 4The common charging of cut is a liquid under pressurized conditions, need not solvent or thinner.If under normal circumstances, selected catalyzer is gas (BF for example 3Deng), after introducing reactor, usually gas phase catalyst partially or completely is dissolved in the liquid of pressurization.Polymerization pressure is usually from 25-500, preferably from 100-300kPa.
Tend to make functionality to reduce because temperature is too high, so polymerization temperature is quite important.Usually polymerization temperature-100 ℃ and+10 ℃ between.Preferably, be lower than-10 ℃ temperature,, preferably between-80 ℃ and-20 ℃, for example carrying out polymerization at-50 ℃ preferably below-20 ℃.Control the temperature of liquid reaction mixture by the means of routine.Should select specific temperature of reaction, so that obtain targeted activity polymeric performance, and, preferably can not allow temperature value depart from selected value+or-5 ℃, simultaneously, change the feeding rate of catalyzer and/or promotor, obtaining desirable Mn, thus the change of monomer distribution in the compensation feed component.
In minute average polymerization time can be from 10-120 minute, preferably from 15-45 minute, more preferably from 15-30 minute, most preferably from 15-25 minute.
The friedel-crafts alkylated reaction will carry out under the required the same terms of formation carbon cation polymerization system.Thereby these conditions right and wrong Changshu are to those skilled in the art known.In addition, the friedel-crafts alkylated reaction is the reaction of knowing, and the reference of the example of conditions suitable and other example for example can be at " advancing organic chemistry " (" Advanced Orgamic Chemistry " (third edition 1-13 chapter of J.March, Wiley, 1985) find in.Typical condition relates to some temperature control mode of removing reaction heat, solvent and the means (stirring etc.) that make the reagent contact.
Being used to make the material of reaction quenching is conventional material, and comprises and be used as cationoid polymerisation promotor (for example water, alcohol) identical materials usually, and different is, with these materials of excessive use, so that make catalyst deactivation.Therefore, although can use the quenching medium that can make any consumption of catalyst deactivation effectively, can be contemplated that described significant quantity will be enough to obtain quenching medium to the mol ratio of catalyzer usually from 1: 1 to 100: 1, preferably from 3: 1 to 50: 1, most preferably from 10: 1 to 30: 1.By being introduced, quenching medium carries out quenching in the polymer product.Usually, be enough to avoid under other component evaporable pressure condition of any gas phase catalyst (if using catalyzer) and mixture between cold snap polymer product being remained on.Temperature for quenching medium is very not crucial, for example can be room temperature or lower temperature.In batch systems, can in reactor, carry out quenching, perhaps preferably after from reactor, taking out product, it is carried out quenching.In continuous system, by being after product is discharged reactor, to carry out quenching.After quenching, usually make polymerisate stand the conventional arrangement step of sodium hydroxide/water washing that comprise with the extracting catalyst residue, wherein the catalyzer of passivation and extraction is in the isolating hydrocarbon of aqueous phase/aqueous phase separation step with remove the water-washing step of residual volume catalyst neutralisation.Then, in debutanizing tower, polymkeric substance is carried out common stripping, thereby remove the volatile monomers of end reaction, further carry out stripping then to remove lightweight polymeric (C for example 24Polymkeric substance).Then, pass through N 2Stripped polymkeric substance is carried out common drying.
Although can during preparation carbon cation polymerization system, introduce one or more aromatic nucleus systems in principle,, when the Living Cationic Vinyl Polymerization system has exhausted the monomer of supply, made the product of better qualification.Depend on active polymerization system to the ratio of one or more aromatic nucleus system consumptions and depend on the functionality of initiator system, can make the polymkeric substance with following performance: the end at polymer chain had end functional groups (1: 1; Simple function), one or more aromatic nucleus systems of the two or more Living Cationic Vinyl Polymerization systems of coupling (so-called side chain or star branched chain polymer that makes with for example 2: 1 or bigger ratio; Simple function), increase Living Cationic Vinyl Polymerization system (the so-called telechelic prepolymer that for example makes of end (termini) end envelope with 2: 1 ratio (difunctionality) or 3: 1 (trifunctionals) etc. at some or each; ), even when using multifunctional initiator wherein one or more aromatic nucleus systems not only as coupling agent but also as the mixed system of end functional groups.Its example includes but not limited to: the mAr-P-I of I-P-ArI-P-Ar-(P-I) nAr-P-I '-(P-Ar) "-P-Ar-P-I "-the P-Ar formula in Ar represent one or more aromatic nucleus systems, P represent polymkeric substance (available from, homopolymer, random or segmented copolymer etc.), I represents the simple function initiator, and I ' represents multifunctional initiator, I " the expression bifunctional initiator; n and m for respectively with one or more aromatic nucleus systems, or the corresponding to number of the functionality of multifunctional initiator.
Preferably, the telechelic prepolymer is by one or more end functional groups and side chain or star branched chain polymer end-blocking and by the coupling of one or more multifunctional coupling agent institute, wherein said end group and described multifunctional coupling group are Wuyuan, the heterocycle of six-π-electronics.Described side chain or star branched chain polymer are preferably by one or more end functional groups end-blockings, and wherein said end group is Wuyuan, the heterocycle of six-π-electronics.
Telechelic prepolymer and side chain or star branched chain polymer, particularly be can be used for preparing the high-molecular weight product, comprised network and VI (viscosity index) properties-correcting agent more than end capped those materials of end functional groups.
Reaction product replacement of the present invention or unsubstituted, except that VI properties-correcting agent, can also be as dispersion agent or the oxidation inhibitor in the lubricating oil for example.Therefore, the invention provides a kind of lubricating oil composition, said composition comprises: the lubricated crude oil of a large amount of (greater than 50% weight) and a small amount of (being less than 50% weight) be preferably from 0.1-20% weight, especially from the replacement of the present invention of 0.5-10% weight or unsubstituted reaction product (active substance); Weight percent wherein is in the gross weight of composition.
By additive packing is added in the lubricating oil, can produce lubricant formulations.If final lubricant formulations is many grades form, so wherein can comprise a small amount of viscosity modifier.The kind and the consumption that are used for the lubricant formulations additive packing depend on final purposes, described purposes can comprise: the oil engine of spark ignition and ignition comprises: automobile and truck engine, the diesel motor of ship and railway, gas engine, fixed generator and turbine.
Lubricant formulations is mixed, so that satisfy in the U.S. by SAE (SAE) performance requriements that the tripartite arrangement between American Petroleum Institute (API) (API) and the American Standard of Testing Materials (ASTM) is classified.In addition, AAMA (AAMA) and company limited of JAMA (JMMA), by so-called international lubricant level and evaluation committee (ILSAC), unite the minimum performance standards of having formulated the private car engine oil that is used for gasoline as fuel.
In Europe, confer by Association des Constructeurs Europeens del ' Automobile (ACEA) and Technical Committee of petroleum additive manufacturers (ATC) and Association Technique de l ' Industries Europeens desLubrifants (ATIEL) and to have worked out the engine oil classification.Except that the oil classification system of these international endorsements, even be not all but also have many Original equipment manufacturers (OEMs)s that its oneself internal performance requirement is arranged, being used for first the lubricant formulations that (being factory) fill for these performance requriementss must satisfy.
Proper lubrication crude oil is natural, mineral or synthetic lubricating oil.
Natural lubricating oil comprises animal oil and vegetables oil, as Viscotrol C.Mineral oil comprises by crude oil, naphthenic or paraffinic or its mixture, coal or the shale lubricating oil distillate of deriving and obtaining for example, and these cuts may live through some processing, as clay-acid, solvent or hydrogen treatment.
Ucon oil comprises: for example by the derive synthetic polymer of the hydrocarbon that obtains of the alkylene oxide polymer of poly-alpha olefins, isomerized slack wax, modification and ester, described these materials are known in the prior art.Preferably, these lubricating oil are the crankcase lubrication oil formulas that are used for spark ignition and compression ignition engine, but also comprise the lubricant of Vulcan gear, metal working fluid and automatic transmission liquid.
Preferably, the lubricated set of crude oils of thing combined according to the invention becomes the mixture of mineral lubricating oils or mineral lubricating oils, as the product of selling with trade(brand)name " HVI " by Royal Dutch branch office/company of Shell Group, or by the synthetic hydrocarbon crude oil of Royal Dutch branch office/company of Shell Group with trade(brand)name " XHVI " (trade mark) sale.
The viscosity that is present in the lubricated crude oil in the present composition can change in wide region, and usually from 3-35mm 2/ s (100 ℃).
Can include various other additives well known in the prior art according to lubricating oil composition of the present invention, as: (a) viscosity index improver or properties-correcting agent.Viscosity modifier can be solid-state or the natural or synthesis material of enriched material shape, and may be defined as the normally material of polymkeric substance, by introducing viscosity modifier or improving agent, will substantially improve (available from least 5 units) viscosity index (available from what measure) by ASTM method D2270.These materials can all be introduced in the final lubricant formulations, thereby obtain the desirable performance of lubricant formulations.The example of described viscosity modifier is: the linearity of diene or star polymer, described diene such as isoprene or divinyl; Or described diene and replacement or unsubstituted cinnamic multipolymer.These multipolymers are suitable is segmented copolymer and preferably is hydrogenated with such degree, so that make most unsaturated fractional saturations of alkene.The known in the prior art viscosity modifier that many other kinds are arranged, and the overwhelming majority is described in the minutes " many grades engine oil viscosity and flowing property " (Esslingen, Germany, 1977.12).In addition, it is also known that in prior art, it is functionalized that viscosity modifier is carried out, so that (for example introduce dispersiveness, dispersant viscosity index improvers based on segmented copolymer or polymethacrylate) and/or oxidation inhibitor functionality and viscosity modifying function, and they also can have the pour point reducer of sneaking into, so that obtain machinable product in cold climate.(b) ashless or contain grey extreme pressure additive/wear preventive additive, as comprise the phosphorodithioic acid salt or the ash-free dithiocarbamates class of metal, and composition thereof.The real composition of each composition will change according to final purposes, therefore, can be based on a metalloid ion and various alcohol, wherein alkyl and aromatic portion all can change size.Preferably zinc dithiophosphate (ZDTPs) or phosphorodithioic acid sodium.(c) dispersion agent includes the succinimide and the mannich base of various molecular weight and amine kind, includes borate (ester) class, the ester class of perhaps also various kinds and molecular weight.Ashless dispersant preferably, the succinimide that replaces as polyolefine, for example, at the dispersion agent described in the GB-A-2231873.(d) oxidation inhibitor, amine type oxidation inhibitor for example is as " IRGANOX " (trade mark) L57 (uncle C 4-C 12The soluble copper compound of alkyl diphenylamine phenol type when " IRGANOX " (trade mark) L135 (2,6-di-t-butyl-4-(2-carboxyl (alkyl) ethyl) phenol) (available from, CIBA Speciality Chemicals) or copper concentration are between 50-500ppm.(e) for example, the antirust compound of ethylene/propylene alkene block copolymer class.(f) the friction properties-correcting agent used of fuel economy, or comprise metal (available from molybdenum), or metal-free ester class and amine, or the synergistic mixt of these properties-correcting agent.What (g) comprise metal goes the trowel used for plastering agent, as phenates class, Sulfonates, salicylic acid salt or naphthenic acid salt, or its mixture, all these stain removers can be neutral or overbasic, described overbasic stain remover is a carbonate, oxyhydroxide class or its mixture.Described metal is preferably calcium, magnesium or manganese, but also can use basic metal, as sodium or potassium.(h) copper passivator is preferably the triazole species of alkylating or benzylization.
Reaction product of the present invention also can be used as the additive of fuel, for example is used as the dispersion agent of detergent additive.Therefore, the present invention also provides a kind of fuel composition, described composition comprises in a large number basic fuel and a small amount of (being less than 50% weight) of (greater than 50% weight), preferably from 0.001-2% weight, more preferably from 0.001-0.5% weight, especially preferred is reaction product of the present invention from 0.002-0.2% weight (actives), and percentage number average wherein is in the gross weight of composition.
Suitable basic fuel comprises gasoline and diesel oil fuel.That these basic fuel can comprise is saturated, the mixture of alkene and aromatic hydrocarbon, and can comprise for example sulphur of 0.001-0.1% weight.They can be derived by following material and obtain: straight-run spirit, synthetic aromatic hydrocarbon mixture, heatable catalytic cracked hydrocarbon feed, the petroleum fractions of hydrocracking or the hydrocarbon of producing of catalytic reforming.
Can comprise various additive well known in the prior art according to fuel composition of the present invention, as: (a) antiknock dope, as lead compound, or other compound is as three carbonyl methyl cyclopentadienyl manganese or adjacent azidophenyl methyl cyclopentadienyl manganese.(b) help-octane promoter, as benzoyl acetone.(c) cleaning agent, as following commercially available prod: " NALCO " (trade mark) EC5462A (available from Nalco), " TOLAD " (trade mark) 2683 (available from Baker Petrolite), EXP177, EXP159M, EXP175, EP409 or EP435 (available from, RESpeciality Chemicals), and T9360-K, T9305, T9308, T9311 or T327 (available from Baker Petrolite).(d) defoamer, as following commercially available prod: " TEGOPREN " (trade mark) 5851, Q25907, MR1027, MR 2068 or MR2057 (available from Dow Corning Corporation), " RHODORSIL " (trade mark) (available from Rhone Poulenc) and " WITCO " (trade mark) SAGTP325 or SAG327 (available from Witco).(e) igniting properties-correcting agent (for example, nitric acid 2-ethylhexyl ester, nitric acid cyclohexyl ester, di-t-butyl peroxide and walk to the material described in the 3rd hurdle the 21st row on US-A-4208190 the 2nd hurdle the 27th.(f) rust-preventive agent is (for example by Rhein Chemie (Mannheim, Germany) commodity of selling with " RC 4801 ", or the polyol ester of succinic acid derivative, described succinic acid derivative at least one position of its alpha-carbon atom, have unsubstituted or replace, from the aliphatic hydrocarbon group of 20-500 carbon atom (for example pentaerythritol diester of the succsinic acid that replaces of polyisobutene)).(g) reodorant.(h) wear preventive additive.(i) oxidation inhibitor (for example, phenol, as 2,6 di t butyl phenol, or phenylenediamine,, N '-two sec-butyls-p-phenylenediamine) as N.(j) metal passivator.(k) lubricant, as following commercially available prod: EC831, " PARADYNE " (trade mark) 631 or 655 (available from Paramins) or " VEKTRON " (trade mark) 6010 (available from Shell AdditivesInternational Limited).(l) carrier fluid, as polyethers, C for example 12-C 15(these products can derive from Royal Dutch branch office/company of Shell Group to the propylene glycol that alkyl replaces, by C for " SAP 949 ", " HVI " or " XHVI " (trade mark) crude oil 2-C 6The polyolefine that monomer derived obtains for example has the polyisobutene of 20-175, a particularly 35-150 carbon atom; Or poly-alpha olefins, the viscosity of described poly-alpha olefins in the time of 100 ℃ is from 2 * 10 -6To 2 * 10 -5m 2/ s (2-20 centistoke), and be the hydrooligomer that comprises the 18-80 carbon atom of deriving and obtaining by the 'alpha '-olefin monomers of at least a 8-18 of comprising carbon atom.
Can be by the present invention's replacement or unsubstituted reaction product be added into lubricated crude oil or make lubricating oil composition of the present invention and fuel composition in the fuel substantially.For simplicity, with the enriched material of additive and lubricated crude oil and basic blending of fuel.Described enriched material comprises usually: the additive of inertia carrier fluid and one or more conc forms.Therefore, the present invention also provides multifunctional additive for lubricating oils, and described enriched material comprises: inertia carrier fluid and 10-80% weight (actives), the present invention replace or unsubstituted reaction product, and wherein percentage ratio is in the gross weight of enriched material.
The example of inertia carrier fluid comprises: the mixture of hydro carbons and hydro carbons and alcohol or ether, and as methyl alcohol, ethanol, propyl alcohol, butoxy ethanol or methyl tertiary butyl ether.For example, carrier fluid can be an aromatic hydrocarbon solvent, as toluene, and dimethylbenzene, the mixture of its mixture or toluene or dimethylbenzene and alcohol.In addition, carrier fluid can be the mixture of mineral crude oil or mineral crude oil, as the product of selling with trade(brand)name " HVI " by Royal Dutch branch office/company of Shell Group, " HVI 60 " crude oil for example, or the synthetic hydrocarbon crude oil of selling with trade(brand)name " XHVI " (trade mark) by Royal Dutch branch office/company of Shell Group.
The indefiniteness example of suitable additive concentration in the lubricating oil composition of final blending:
Oil ingredient % quality ?????A ?????B ?????C ?????D ??????E ???F
The alkaline earth metal sulfonate stain remover ????3.8 ????3.4 ????- ????- ?????- ???-
The alkaline earth phenolates stain remover ????1.2 ????1.1 ????- ????- ?????- ???-
Alkaline-earth metal salicylate stain remover ????- ????- ????4.6 ????2.5 ?????3.6 ???10.5
High molecular weight dispersant ????- ????5.5 ????8.0 ????5.0 ?????11.5 ???-
The lower molecular weight dispersion agent ????6.0 ????2.0 ?????- ????- ?????- ???9.0
Main ZDTP ????0.5 ????- ?????- ????0.3 ?????- ???0.7
Inferior ZDTP ????0.4 ????1.0 ????0.9 ????0.7 ?????1.2 ???0.6
Amine antioxidants ????- ????- ????0.6 ????0.8 ?????0.3 ???-
Phenolic antioxidant ????0.7 ????1.2 ????- ????- ?????- ???-
Crude oil Surplus Surplus Surplus Surplus Surplus Surplus
The indefiniteness example that is used for the suitable additive concentration of blending lubricating oil composition:
Oil ingredient % quality ????A ????B ????C ????D ????E ????F
The alkaline earth metal sulfonate stain remover ????29.9 ????23.8 ????- ????- ????- ????-
The alkaline earth phenolates stain remover ????9.4 ????7.7 ????- ????- ????- ????-
Alkaline-earth metal salicylate stain remover ????- ????- ????32.4 ????26.6 ????21.6 ????50.2
High molecular weight dispersant ????- ????38.5 ????56.3 ????53.2 ????68.9 ????-
The lower molecular weight dispersion agent ????47.2 ????14.0 ????- ????- ????- ????43.1
Main ZDTP ????3.9 ????- ????- ????3.2 ????- ????3.3
Inferior ZDTP ????3.1 ????7.0 ????6.3 ????7.4 ????7.2 ????2.9
Amine antioxidants ????- ????- ????4.2 ????8.5 ????1.8 ????-
Phenolic antioxidant ????5.5 ????8.4 ????- ????- ????- ????-
Crude oil Surplus Surplus Surplus Surplus Surplus Surplus
In addition, the present invention also provides replacement of the present invention or the unsubstituted reaction product purposes as dispersion agent, stain remover or oxidation inhibitor additive.
The following examples will illustrate the present invention.Embodiment 1-5 is a model trial.They use by 2-chloro-2,4, the activated carbon cationic dimeric system (therefore being similar to the iso-butylene dimer) that the 4-trimethylpentane is derived and obtained, rather than the Living Cationic Vinyl Polymerization system is as reagent.Embodiment 6-10 explanation is with the of the present invention product of polyisobutene as polymeric component.At last, embodiment 11 relates to the antioxygen test of thiophene-functionalized PIB, the illustrative purposes of the novel product of the present invention, and embodiment 12 has illustrated the dispersing property of functionalized PIBs.
Usually, each embodiment carries out in being dipped in the batch reactor of exterior cooling in bathing.Solvent and reagent are carried out finish-drying.Abbreviation below using in an embodiment:
CTMP 2-chloro-2,4, the 4-trimethylpentane
Tmb 1,1,3,3-tetramethyl butyl (radical)
PIB polyisobutene or its radical
The IB iso-butylene
The MCH methyl cyclohexanol
The DCM methylene dichloride
MeOH methyl alcohol
The TH thiophene
BrTH 2-bromothiophene
MeTH 2-thiotolene
BTH 2,2 '-dithienyl
DBTH 3-dodecyl-2, the 2-dithienyl
DTHCE 1,1-two (2-thienyl)-2,2,2-trichloroethane
The FU furans
Me-FU 2-methyl furan
DtBP 2, the 6-di-tert-butyl pyridine.
Synthetic DBTH
Reaction by 3-bromine BTH and dodecyl bromination magnesium makes DBTH.3-bromine BTH is 1, and under the existence of 1 '-two (diphenylphosphino) ferrocene, the reaction by 2-thiophene magnesium bromide and BrTH makes.
Embodiment 1
In the three neck round-bottomed flasks (250ml) that magnetic stirrer is housed, add 305mg (2.05mmol) CTMP, add 40ml60: 40v/vMCH/DCM and 1385mg (10.02mmol) cis-naphthalane (decaline) (interior mark) then.Then with this reactor cooling to-80 ℃, add 1869mg (9.85mmol) then and be dissolved in TiCl among the 40ml MCH/DCM 4Then, interpolation 90mg (1.07mmol) is dissolved in the TH among the 20mlMCH/DCM.Take out the 2ml sample then at set intervals, and utilize MeOH to carry out quenching, and analyze by gas-liquid chromatography at-80 ℃.
GLC shows end capped and the link coupled product, 2-(tmb) TH (I) and 2, degree of conversion and ratio between 5-two (tmb) TH (II).After 2 hours, degree of conversion reaches 60% (at the TH of ingress), and product ratio I/II is 83/17.After stirring is spent the night, make mixture heating up to room temperature, be 54/36 o'clock at ratio, transformation efficiency reaches 97.4%.
Embodiment 2
Under the condition identical, when substituting TH, do not react with 1.28g (10mmol) 2-ethanoyl TH with embodiment 1.Obviously, the 2-Acetyl Groups is a deactivating group.
Embodiment 3
Under the condition identical, when substituting TH, 1.32 gram 2-methyl-5 (tmb) FU in half an hour, have been made with 0.82g (10mmol) Me-FU with embodiment 1.Analytical data below having obtained: 1H-NMR (300 MHz, CDCl 3): 0.76 (s, 9H), 1.29 (s, 6H), 1.63 (s, 2H), 2.26 (d, 3H), 5.82 (m, 2H); 13C-NMR (75 MHz, CDCl 3): 14.0,30.1,31.2,32.0,5.9.54.8,104.0,106.0,150.1,161.4 ppm.
Embodiment 4
In the three neck round-bottomed flasks (250ml) that magnetic stirrer is housed, add 7.55g (51mmol) CTMP, add 5.0g (51mmol) then and be dissolved in MeTH among the 20mlDCM.Add 0.870g (6.13mmol) BF at leisure 3OEt 2And reaction is analyzed by GLC.According to the GLC data, after adding Lewis acid, form the monoalkylated product that wherein forms a small amount of dialkyl group product immediately.
To crude product wash, dry and part distillation (kugelrohr).Found that 19% MeTH changes into 2-methyl-5 (tmb) TH.
Embodiment 5
According to the step of embodiment 1, use 0.555g (3.75mmol) to be dissolved in 10ml40: 60v/v hexane: the CTMP among the DCM; 3.55g (18.75mmol) be dissolved in TiCl in the described solvent of 20ml 4And 0.60g (1.875mmol) is dissolved among the DBTH in the described solvent of 20ml.The process of the GC assaying reaction at the independent peak by wherein finding two identical sizes, and show the relation of DBTH of (passing through GC-MS) 5-(tmb) DBTH and 5 '-(tmb).Realized 75% transformation efficiency.
Embodiment 6
Utilize TH, BrTH, MeTH, DTHCE, DBTH, FU and MeFU have carried out the test of PIB-functionalization.
At-78 ℃, by utilizing CH 2Cl 2/ hexane solvent mixture carries out the polymerization of iso-butylene with simple laboratory polymerization process.After reaching high (about 100%) monomer conversion, add the aromatic nucleus system.GPC operating period by UV spectroscope detector and pass through 1The change that H NMR spectroscope has recorded end structure.
As follows with the end capped test conditions of BrTH: reactor is equipped with 6.2mmolCTMP, 5.2mmol2,2 ' bipyridyl, 150mlCH 2Cl 2With the 350ml hexane.Described solution is cooled to-78 ℃, add 5ml IB then, and 100ml is dissolved in CH 2Cl 2TiCl (0.18M) 4After 5 minutes and 10 minutes, add 4ml IB again.When polymerization is finished, 31mmol is dissolved in 100ml (pre-cooled) CH 2Cl 2In BrTH be added in the reaction mixture and monitoring reaction (utilize pre-cooled methyl alcohol as quenchant) every now and then.
As follows with the end capped test conditions of MeTH: reactor is equipped with 3.6mmolCTMP, 2.4mmol2,2 ' bipyridyl, 50mlCH 2Cl 2With the 140ml hexane.Described solution is cooled to-78 ℃, add 5ml IB then, and 50ml is dissolved in CH 2Cl 2TiCl (0.24M) 4After 5 minutes and 10 minutes, add 5ml IB again.When polymerization is finished, 10mmol is dissolved in 50ml (pre-cooled) CH 2Cl 2In MeTH be added in the reaction mixture and monitoring reaction (utilize pre-cooled methyl alcohol as quenchant) every now and then.
BrTH will make the end of the chain Quantitative yield of polyisobutene (PIB) become corresponding heterocycle functionality with MeTH.Reaction between the carbocation end of the chain and these compounds is a quickish process; The UV analysis revealed utilizes BrTH to carry out Quantitative yield in 30-45 minute, correspondingly utilizes the MeTH Quantitative yield time to be 10-20 minute.
1H NMR spectrum demonstrates following signal: for 2-bromo-thiophene, 6.55 (d, 2H), 6.80 (d, 2H); For 2-methyl-thiophene, (d, 2H), 6.55 (d, 2H), this spectrum shows, has formed the corresponding end of the chain when utilizing BrTH and MeTH to carry out functionalization respectively 6.50.It should be noted that will demonstrate fragrant signal for the heterocycle end of the chain, and for utilizing not nucleophilic reagent with the reaction of the positively charged ion end of the chain to carry out being used for three generations's chlorine terminated-CH among the PIBs of quenching 2-group characteristic, at the 1.94ppm place without any signal.Spectroscopical result (UV and NMR) has shown the quantitative end quenching that utilizes BrTH and MeTH.
Also attempt to carry out the coupling of active PIB chain by dithienyl.The UV signal indicating of GPC adds dithienyl effectively and is bonded on the end of the chain.Yet the coupling phase of the chain that its molecular weight neither causes with DBTH is consistent, and also the coupling phase of the chain that does not cause with DTHCE is consistent.In the presence of DBTH, polymerization system is heated to room temperature also can cause coupling.
Also find by test in advance in addition, furans and 2-methyl furan also will with active PIB chain reaction.
Embodiment 7
Utilize 33mmolCTMP, 49mmolDtBP and 131mmolTiCl 4As initial system; 600ml 60: 40v/v MCH/DCM carries out isobutene polymerisation as solvent and 1114mmol IB at-78 ℃.After 1 hour, add 31mmolMeTH.Found that in 30 minutes and Quantitative yield to be become 2-methyl-5 (PIB) TH.
Embodiment 8
Utilize 16.5mmolCTMP, 4.2mmolDtBP and 63mmolTiCl 4As initial system; 600ml 60: 40v/v MCH/DCM carries out isobutene polymerisation as solvent and 604mmol IB at-78 ℃.The number-average molecular weight of formed polymkeric substance is 2244.After 1 hour, add 7.3mmolTH.Found that in 30 minutes Quantitative yield will take place.Product is measured, comprised 2-(PIB) TH (Mn is 2575) and 2-5-two (PIB) TH (Mn is 3121).
Embodiment 9
Utilize 16.8mmolCTMP, 24mmolDtBP and 65mmolTiCl 4As initial system; 600ml 60: 40v/v MCH/DCM carries out isobutene polymerisation as solvent and 566mmol IB at-78 ℃.0.5 after hour, add 21mmol MeFU.Found that in 30 minutes and Quantitative yield to be become 2-methyl-5 (PIB) FU.
Embodiment 10
Utilize 60mmol CTMP, 30.1mmol 2,2 '-bipyridyl and 562.5mmolTiCl 4As initial system; 1200ml 60: 40v/vMCH/DCM carries out isobutene polymerisation as solvent and 916mmol IB at-78 ℃.After 1 hour, take out 50% solution.In rest solution, add 60mmol ethyl-2-thiophene acetic acid ester.After 2 hours, GPC, 1H and 13C-NMR has confirmed the existence of desirable functionalized PIB.
Embodiment 11
Utilize isothermal differential scanning calorimetric (DSC) analytical method, make the oil for preparing fully (comprise dispersion agent, stain remover, as the zinc dithiophosphate of extreme pressure anti-wear agent and 1% weight, Mn be respectively 1500 and 3500, the end capped PIB of 2-thiotolene base) stand the antioxygen test.
Described analysis utilizes two Mettler-Toledo instruments (DSC27HP) and carries out.Therefore, 2.00 ± 0.05mg sample is placed aluminium dish and be loaded into the DSC device.Then, utilize Brooks pressure and mass rate controller, oxygen is pressed and flow velocity is arranged to 3.4MPa (500psig) and 60 standard ml/ minutes.Lead control by override Dou, sample is heated to 200 ℃ of test temperatures rapidly.Then, the output of monitoring power remains on test temperature with sample simultaneously.The tangent line by measuring exothermic peak upthrow side maximum slope point and the intercept of baseline are measured inductive phase, and described exothermic peak identifies by the derivative that measures enthalpogram and baseline.
Compare with 10.9 minutes average inductive phase of the oil that does not have the end capped PIB of 2-thiotolene base to prepare, this test shows that be respectively 13.7 and 13.6 minutes the average inductive phase of sample.
In other words, the end capped PIBs of these 2-thiotolene bases is effective oxidation inhibitor.
Embodiment 12
Product (Mn=3180 with embodiment 10; 3.0mmol) and N, N-dimethyl-1,3-diaminopropanes (DAP; 150mmol) place the three-necked flask that reflux exchanger is housed, and 130 ℃ of heating 10 hours.Under vacuum, remove excessive DAP.Utilize hexane (60ml) to dilute resulting reaction mixture, and (3 * 30ml) wash with methyl alcohol.At MgSO 4Last dry organic layer also filters.Remove and desolvate, stayed high viscosity material.Productive rate: 75%.
13C-NMR: respectively 170.1,157.7,133.4,126.5 and 122.2ppm, and 58.8,58.4 and the 45.3ppm place the tangible signal of bonding thienyl and bonding DAP carbon appears.
IR: at 1660cm -1The tangible signal of amidocarbonylation appears in the place, does not have ester carbonyl group.
Ultimate analysis: 1.07% weight N, 0.90% weight S.
Utilize Bohlin VOR (Viscometry-Oscillation-Relaxation) rheometer,, make the product of embodiment 12 stand dispersivity test in the mode of its viscometry.Utilize hot plate and magnetic splash bar, sample (25 gram) is mixed in the HVI-65 NS crude oil at 60-85 ℃.Activity substance content is 2% weight.Weighing 1.25 gram carbon blacks (Cabot Vulcan XC72R) add in the Schott bottle of 150ml, and the hot mixing oil that will utilize splash bar to make are poured on the carbon black and allow it drain.Lid covered on bottle and with it be delivered in the heating and stirring device of being arranged to 100 ℃, in this device, make it to reach thermal equilibrium and stir.Then hot sample is poured in the geometric heat cup of rheometer, by with the contrast of reference coupon it being measured, described reference coupon is: at 0.2s -1Under the shearing rate, the viscosity that will contain the carbon black prescription reduces by 66%.
In other words, these functionalized PIBs are effective dispersion agent.

Claims (15)

1. the functionalized novel method of a polymkeric substance for preparing by the carbocation catalyzed polymerization is wherein reacted activated carbon cationic polymerization system and one or more aromatic nucleus system.
2. the method for claim 1, wherein one or more aromatic nucleus systems are selected from: five-, six-, or seven-atom heterocycle.
3. method as claimed in claim 2, wherein one or more aromatic nucleus systems are: comprise one or more nitrogen that are selected from, oxygen, the heteroatomic heterocycle of p and s.
4. method as claimed in claim 1 or 2, wherein one or more aromatic nucleus systems are selected from: six-π-electronics member ring systems.
5. the described method of each claim as described above, wherein one or more aromatic nucleus systems are selected from: heterocyclic pyrroles, furans, thiophene, oxazole, isothiazole, 1,3,4-thiadiazoles and pyrazoles, be selected from: the kind that these heterocyclic replace, and be selected from: replace and unsubstituted (benzo-) condensed ring system, precondition is, substituting group neither hinders the remaining activity site of aromatic nucleus system on the space, also not passivation aromatic nucleus system.
6. the described method of each claim as described above, wherein one or more aromatic nucleus systems are selected from: heterocyclic pyrroles, furans, thiophene, and be selected from: the kind that these heterocyclic replace, precondition is that substituting group neither hinders the remaining activity site of aromatic nucleus system on the space, also not passivation aromatic nucleus system.
7. as claim 5 or 6 described methods, wherein, substituting group is: amino, hydroxyl, alkoxyl group, aminocarboxyl, alkyl or aryl group, or halogen atom.
8. by the end capped telechelic prepolymer of one or more end functional groups, wherein end group is five-atom, six-π-electron heterocycles system.
9. by the polymkeric substance of one or more multifunctional coupling group link coupled side chains or star-side chain, wherein multifunctional coupling group is five-atom, six-π-electron heterocycles system.
10. as claimed in claim 9, by the polymkeric substance of the end capped side chain of one or more end functional groups or star-side chain, wherein multifunctional coupling group is five-atom, six-π-electron heterocycles system.
11. a lubricating oil composition comprises: the replacement or the unsubstituted reaction product of lubricated in a large number crude oil and a small amount of each method of claim 1-7.
12. a fuel composition comprises: the replacement or the unsubstituted reaction product of a large amount of basic fuel and a small amount of each method of claim 1-7.
13. a multifunctional additive for lubricating oils comprises: inertia carrier fluid and in the replacement or the unsubstituted reaction product of enriched material total amount from each method of 10-80% weight claim 1-7.
14. the replacement of each method of claim 1-7 or unsubstituted reaction product be as dispersion agent, the purposes of stain remover or antioxidant additive or VI properties-correcting agent.
15. the telechelic prepolymer described in claim 8 or the polymkeric substance of the side chain described in claim 10 or star-side chain comprise the purposes in network and the VI properties-correcting agent in the preparation high molecular weight product.
CN98801424A 1997-08-19 1998-08-19 Functionalized polymers Pending CN1241195A (en)

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PCT/EP1998/005472 WO1999009074A1 (en) 1997-08-19 1998-08-19 Functionalized polymers

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