CN1241195A - Functionalized polymers - Google Patents

Abstract

The present invention discloses a novel method for functionalization of polymers prepared by carbocation-catalyzed polymerization, wherein an activated carbocation-catalyzed polymerization system is reacted with one or more aromatic ring systems, and the substituted or unsubstituted Use of the reaction product of the product in lubricating oil or fuel compositions and additive concentrates, for example as dispersants, detergents or antioxidant additives or VI modifiers.

Description

functionalized polymer

The present invention relates to a novel method of functionalizing polymers prepared by carbocation-catalyzed polymerization and to novel functionalized polymers, such as telechelic prepolymers.

Polymers with functional groups can be used as lubricating additives, compatibilizers, emulsifiers or as raw materials for the production of adhesives, modifiers, coatings, sealing materials, etc. Therefore, there has been a strong interest in functionalizing polymers.

Carbocation-catalyzed polymerization is one of the known methods of preparing functionalized polymers. For example, WO-A-94/13706 discloses a direct synthesis by living cationic catalyzed polymerization of novel polymeric materials functionalized with nitrogen-containing functional groups. Here, polymerization and functionalization take place in a substantially simultaneous manner (available from, as a one-step Friedel-Crafts reaction). In the textbook "Structural Polymers by Carbocationic Macromolecular Engineering: Theory and Practice" ["Designed Polymers by Carbocationic Macromolecular Engineering: Theory and Practice" (Hanser Publishers, 1991)], Section II.5.2., the authors J.P.Kennedy and B. Ivan provides many examples with auxiliary end groups not only in polyolefins but also in poly(alkyl vinyl ethers), but usually prepared in a two-step process.

It will be appreciated that polymers with novel end groups and the potential for further reactions prepared by one-step carbocationically catalyzed polymerization would be particularly desirable.

Accordingly, a method has been found for the functionalization of polymers prepared by carbocation-catalyzed polymerization in which an activated carbocation-catalyzed polymerization system is reacted with one or more aromatic ring systems.

This method will be particularly suitable when one or more aromatic ring systems are selected from five-atom, six-atom, or seven-atom heterocyclic rings. The heterocycle will contain one or more heteroatoms selected from N, O, P and S and will often provide the electron-rich environment required for the reaction to take place, the Friedel-Crafts reaction. Preferably, the one or more aromatic ring systems are selected from six-π-electron ring systems. Examples of particularly preferred aromatic ring systems include: pyrrole, furan, thiophene, oxazole, isothiazole, 1,3,4-thiadiazole and pyrazole. These aromatic ring systems may be partially substituted, provided the substituents neither sterically block the remaining reactive sites of the aromatic ring system nor deactivate the aromatic ring system. For example, the substituents may be selected from: amino, hydroxyl, alkoxy, aminocarbonyl, alkyl or aryl groups, or halogen atoms. The first-mentioned substituents are strongly reactive groups. The substituents may be quite large, for example, in the case where the aromatic ring system acts as a coupling agent, the molecular weight of the first substituent corresponds to half the (average) molecular weight of the functionalized polymer. Examples of suitable substituted aromatic ring systems include, for example, 3,3-dimethyl-3H-pyrazole and 2,2-dithienyl.

One or more aromatic ring systems may also be selected from: (benzo-)fused ring systems such as naphthalene, quinoline, quinoxaline, indole, benzofuran, benzothiophene, pteridine, purine, indolizine wait. In addition, these one or more aromatic ring systems may be partially substituted with the same substituents as described above.

Preferably, the one or more aromatic ring systems are selected from the group consisting of pyrrole, furan and thiophene and substituted species thereof. The polymers thus prepared can be further functionalized by the well-known and extensive chemistry of pyrrole, furan and uran structures. An additional advantage of using thiophenes or substituted thiophenes is the inherent antioxidant properties of the functionalized polymers.

It should be noted that the definition of active polymer used throughout the specification is consistent with the definition in WO-A-94/13706 and the aforementioned textbook by Kennedy and Ivan. Thus, living carbocation catalyzed polymerization systems comprise ideal living polymerizations based on cationic initiation in which chain transfer and termination do not occur, and in which chain transfer and/or termination are rapidly reversible and the rates of these processes will be faster than Quasi-living polymerization with fast growth rate. In other words, a system in which the rate of irreversible chain transfer and/or termination is zero or nearly zero.

As discussed in said textbook, (active) carbocation-catalyzed polymers are polymers formed by controlled initiation, i.e. by controlling monofunctional or polyfunctional initiators, whereby the polymer chains will Grow in one direction at one end or in multiple directions from the center.

Suitable active carbocation catalyzed polymerization systems are: for example, tertiary alkyl esters/BCl ₃ ; cumyl acetate/TiCl ₄ ; 2,2'-dipyridyl/TiCl ₄ ; CH ₃ SO ₃ H/SnCl ₄ +n- Bu ₄ NCl; HI/I ₂ ; HI/ZnX ₂ or SnX ₂ (X=Cl, Br ₎ ; HI/ZnI _{2 ;} Dimethyl-1,3-pentadiene; Styrene; p-vinylphenyl glycerol ether; isobutyl vinyl ether; methyl vinyl ether/p-methoxystyrene; or 2- Methyldihydrofuran (for a more comprehensive list see Table IV on pages 43-55 of the aforementioned textbook). In addition, nitrogen-containing compounds used as initiators in WO-A-94/13706, such as 2-azido-isopropylbenzene or bis(2-azido-isopropyl)benzene with di A mixture of ethyl aluminum chloride, TiCl ₄ or BCl ₃ .

Homogeneous catalysts are preferred, although insoluble catalysts can be used. Solvents are generally used during polymerization. Suitable solvents have a freezing point below the preferred polymerization temperature. Exemplary solvents include, but are not limited to: C ₂ -C ₁₀ alkanes, alkenes, alkyl and alkenyl halides, carbon tetrachloride, carbon disulfide, nitroethane, liquid carbon dioxide, and methyl Cyclohexane. In addition, mixed solvents can also be used. Preferred solvents are the low-boiling alkyl halides: methyl chloride, ethyl chloride, propane chloride, n-butyl chloride, and 1,2-dichloroethane; and neopentane, hexane, pentane, and Purified petroleum ether.

Any cationized polymerizable monomer can be used, including linear and branched alpha-olefins, isoolefins, aliphatic monoolefins, cycloaliphatics, styrene derivatives, indene and its derivatives, and in Kennedy's Other monoolefinic and heterocyclic cationized polymerizable monomers identified in the article "Cationic Cationic Polymerization of Olefins: AC Critical Inventory" pp. 39-53 (Wiley, 1975). In addition, vinyl ethers can also be used.

Particularly valuable polymers are obtained from isoolefins of 4 to 20 carbon atoms or mixtures thereof. Examples of the unsaturated hydrocarbon include, but are not limited to: isobutene, 2-methyl-butene, 3-methyl-1-butene, 4-methyl-1-pentene, and β-pinene. Other cationically polymerizable monomers that may be used include heterocyclic monomers such as oxazolines and other known heterocyclic monomers that add polar covalent bonds. If desired, mixtures of cationically polymerizable monomers can be used as starting materials in the polymerization zone. Thus, by using two, three or more of the above monomers, copolymers, terpolymers and higher order copolymers can be prepared. Preferred feedstocks to the polymerization zone include: pure isobutene and mixed feedstocks of _C4 hydrocarbons containing isobutene, such as _C4 fractions obtained from operations such as thermal or catalytic cracking of naphtha. Suitable isobutene feedstocks will generally contain at least 10% and up to 100% by weight isobutene, based on the weight of the feed. The C ₄ fraction which is industrially important and usually suitable as feedstock contains: 10-40% 1-butene, 10-40% 2-butene, 40-60% isobutane, 4-10% n-butane, and up to about 0.5% butadiene, all percentages are by weight of the feed. In addition, the isobutylene-containing feedstock may also contain small amounts of other non- _C4 polymerizable olefinic monomers, such as typically less than 25%, preferably less than 10%, and optimally less than 5%, such as propadiene, propylene and _C5 olefins . The term "polyisobutene" as used in the present invention includes not only homopolymers of isobutene, but also isobutylene and one or more other _C4 polymerizable monomers of the conventional _C4 fraction and usually comprising 3-6, preferably comprising Copolymers of non- _C4 ethylenically unsaturated olefinic monomers of 3 to 5 carbon atoms, with the proviso that, based on the number average molecular weight (Mn) of the polymer, said copolymers comprise: usually at least 50%, preferably at least 65% %, most preferably at least 80% by weight of isobutylene units. Under the specific conditions of the present invention, the selective polymerization of isobutene ensures the above-mentioned minimum content of isobutene.

Preferably, the polymerization medium is substantially nontoxic to the catalyst. For example, the olefin feed can be treated by using molecular sieves and alkaline washing to remove eg mercaptans, water and dienes if desired.

The polymerization reaction can be carried out batchwise, or in a (semi)continuous operation in which a continuous stream of furnish is fed into the reactor and an overflow of polymer slurry or solution is taken for recovery of polymer therefrom. From an operational point of view, the preferred reaction mode is a continuous mode of operation using a continuous flow stirred reactor in which feed is continuously introduced into the reactor and product is continuously withdrawn from the reactor in a controlled manner. However, where more precisely defined (narrow molecular weight distribution) products are produced, batch operation is preferably used.

The amount of catalyst used in the process of the invention can be varied in order to achieve the target number average molecular weight of the polymer. Varying the amount of catalyst can also minimize isomerization, or reduce undesired isomerization. The lower the concentration of the initiator in the reaction phase, the higher the molecular weight of the polymer and vice versa. Controlling the molecular weight of the polymer within the range determined by the molecular weight of the selected target polymer will be especially important when the polymer is intended to be used as a dispersant in lubricating oils. The amount of catalyst used will also affect the conversion rate of olefin monomers and the yield of polymer, and generally higher catalyst amount will lead to higher conversion rate and yield. The catalyst is used in an amount sufficient to render the reaction a "living" cationic polymerization.

To induce linear or chain polymerization rather than ring or branched chain formation, the polymerization reaction is carried out in the liquid phase. If using a feed that is in the gas phase at ambient conditions, it is preferred to control the reaction pressure and/or dissolve the feed in an inert solvent or liquid diluent so that the feed remains in the liquid phase. Typical feeds used as the _C4 fraction are liquid under pressure without the need for solvents or diluents. If, under normal circumstances, the selected catalyst is a gas (eg BF ₃ etc.), the gas phase catalyst is usually partially or completely dissolved in the pressurized liquid after introduction into the reactor. The polymerization pressure is usually from 25-500, preferably from 100-300 kPa.

Polymerization temperature is of considerable importance since too high a temperature tends to reduce functionality. Usually the polymerization temperature is between -100°C and +10°C. Preferably, the polymerization is carried out at a temperature below -10°C, preferably below -20°C, preferably between -80°C and -20°C, for example at -50°C. The temperature of the liquid phase reaction mixture is controlled by conventional means. The specific reaction temperature should be selected in order to obtain the target living polymerization properties, and preferably not allow the temperature value to deviate + or - 5°C from the selected value, while at the same time, the feed rate of the catalyst and/or promoter is changed to obtain the desired Mn, thereby compensating for changes in the distribution of monomers in the feed composition.

The average polymerization time in minutes may be from 10-120 minutes, preferably from 15-45 minutes, more preferably from 15-30 minutes, most preferably from 15-25 minutes.

The Friedel-Crafts alkylation reaction will be carried out under the same conditions required to form the carbocationic polymerization system. Thus, these conditions are very familiar to those skilled in the art. Furthermore, the Friedel-Crafts alkylation reaction is a well known reaction and examples of suitable conditions as well as references to further examples can be found, for example, in J. March, "Advanced Organic Chemistry" ( Found in Chapters 1-13 of the third edition, Wiley, 1985). Typical conditions involve some means of temperature control to remove the heat of reaction, solvent, and means of contacting the reactants (stirring, etc.).

Materials used to quench the reaction are conventional materials and include the same materials commonly used as cationic polymerization accelerators (eg water, alcohols) except that these materials are used in excess to deactivate the catalyst. Thus, while any amount of quench medium effective to deactivate the catalyst may be used, it is contemplated that the effective amount will be sufficient to obtain a quench medium to catalyst molar ratio generally from 1:1 to 100:1 , preferably from 3:1 to 50:1, most preferably from 10:1 to 30:1. Quenching is performed by introducing a quench medium into the polymer product. Generally, the polymer product is maintained under pressure conditions sufficient to avoid volatilization of any gas phase catalyst (if a catalyst is used) and other components of the mixture during quenching. The temperature of the quenching medium is not critical and may be, for example, room temperature or lower. In a batch system, quenching may be performed in the reactor, or preferably the product is quenched after it has been removed from the reactor. In a continuous system, quenching is performed after the product exits the reactor. After quenching, the polymer product is usually subjected to conventional work-up steps including sodium hydroxide/water washes to extract catalyst residues, a hydrocarbon/water phase separation step in which passivated and extracted catalyst is separated in the aqueous phase, and removal of A water wash step in which the residual amount neutralizes the catalyst. Then, in the debutanizer, the polymer is typically stripped to remove unreacted volatile monomers, and then further stripped to remove light polymers (such as _C24 polymers). The stripped polymer was then subjected to the usual drying by _N2 .

Although it is in principle possible to introduce one or more aromatic ring systems during the preparation of the carbocationic polymerisation system, better defined products are produced when the living carbocationic polymerisation system has exhausted its supply of monomers. Depending on the ratio of the active polymerization system to the amount of one or more aromatic ring systems, and depending on the functionality of the initiating system, polymers with the following properties can be obtained: at one end of the polymer chain there is a functional end group (1:1 ; monofunctional), coupling of one or more aromatic ring systems of two or more living carbocationic polymer systems (so-called branched or star-branched polymers prepared in a ratio of, for example, 2:1 or more ; monofunctional), living carbocationic polymerization systems end-blocked at some or each termini (so-called e.g. prepared in a ratio of 2:1 (difunctional) or 3:1 (trifunctional), etc. Telechelic prepolymers;), even when polyfunctional initiators are used, in which one or more aromatic ring systems serve not only as coupling agents but also as mixed systems of functional end groups. Examples include, but are not limited to: I-P-ArI-P-Ar-(P-I)nAr-P-I'-(P-Ar)mAr-P-I"-P-Ar-P-I"-P-Ar where Ar represents a or multiple aromatic ring systems, P represents a polymer (purchased from, homopolymer, random or block copolymer, etc.), I represents a monofunctional initiator, I' represents a multifunctional initiator, and I" represents a bifunctional initiator agent, n and m are numbers corresponding to the functionality of one or more aromatic ring systems, or multifunctional initiators, respectively.

Preferably, the telechelic prepolymer is terminated by one or more functional end groups and branched or star-shaped branched polymers and coupled by one or more multifunctional coupling agents, wherein the end groups And the multifunctional coupling group is a five-atom, six-π-electron heterocyclic ring. The branched or star-branched polymers are preferably terminated by one or more functional end groups, wherein the end groups are five-atom, six-π-electron heterocyclic rings.

Telechelic prepolymers and branched or star-branched polymers, especially those terminated with more than one functional end group, can be used to prepare high molecular weight products, including network and VI (viscosity index) modifiers.

The substituted or unsubstituted reaction products of the invention, in addition to VI modifiers, can also be used, for example, as dispersants or antioxidants in lubricating oils. Therefore, the present invention provides a kind of lubricating oil composition, and this composition comprises: a large amount (greater than 50% by weight) of lubricating crude oil and a small amount (less than 50% by weight) preferably from 0.1-20% by weight, especially from 0.5-10 % by weight of the substituted or unsubstituted reaction product (active substance) of the present invention; wherein the weight percent is based on the total weight of the composition.

Lubricant formulations are produced by adding additive packages to lubricating oils. Small amounts of viscosity modifiers may be included if the final lubricant formulation is in multi-grade form. The type and amount of additive package used in a lubricant formulation depends on the end use, which may include: spark-ignited and compression-ignited internal combustion engines, including: automobile and truck engines, marine and railroad diesel engines, gas engines, Stationary generators and turbines.

Lubricant formulations are blended to meet performance requirements as classified in the United States by a tripartite agreement between the Society of Automotive Engineers (SAE), the American Petroleum Institute (API) and the American Standard for Testing Materials (ASTM). In addition, the American Automobile Manufacturers Association (AAMA) and the Japan Automobile Manufacturers Association Co., Ltd. (JMMA), through the so-called International Lubricant Standards and Accreditation Committee (ILSAC), have jointly developed standards for private automobile engine oils used as gasoline fuels. Minimum Performance Standards.

In Europe, the classification of engine oils has been developed in consultation with the Association des Constructeurs Europeens del'Automobile (ACEA) and the Technical Committee of Petroleum Additive Manufacturers (ATC) and the Association Technique de l'Industries Europeens des Lubrifants (ATIEL). In addition to these internationally recognized oil classification systems, many, if not all, Original Equipment Manufacturers (OEMs) have their own internal performance requirements for which lubricant formulations for the first (ie factory) fill must meet.

Suitable lubricating oils are natural, mineral or synthetic lubricating oils.

Natural lubricants include animal and vegetable oils, such as castor oil. Mineral oils include lubricating oil fractions derived from crude oils such as naphthenes or paraffins or mixtures thereof, coal or shale, which fractions may have been subjected to certain treatments such as clay-acid, solvent or hydrotreating.

Synthetic lubricating oils include, for example, synthetic polymers of hydrocarbons derived from polyalphaolefins, isomerized slack waxes, modified alkylene oxide polymers and esters, which are known in the art of. Preferably, these lubricants are crankcase lubricant formulations for spark ignition and compression ignition engines, but also include hydraulic transmission lubricants, metalworking fluids and automatic transmission fluids.

Preferably, the lubricating base oil of the composition according to the invention consists of a mineral lubricating oil or a mixture of mineral lubricating oils, such as the product sold under the trade name "HVI" by the Royal Dutch division/Shell group of companies, or by the Royal Dutch division /Synthetic hydrocarbon crude oil sold by the Shell group of companies under the trade name "XHVI" (trade mark).

The viscosity of the lubricating base oil present in the composition of the invention can vary within wide ranges, and is generally from 3-35 ^mm2 /s (100°C).

The lubricating oil composition according to the present invention may contain various other additives known in the art, such as: (a) viscosity index improvers or modifiers. Viscosity modifiers may be natural or synthetic materials in the form of solids or concentrates and may be defined as substances, usually polymers, which, by the introduction of viscosity modifiers or improvers, will substantially improve (purchased from at least 5 units ) Viscosity Index (purchased as determined by ASTM method D2270). These substances can all be incorporated into the final lubricant formulation to obtain the desired properties of the lubricant formulation. Examples of such viscosity modifiers are: linear or star polymers of dienes such as isoprene or butadiene; or copolymers of such dienes with substituted or unsubstituted styrene . These copolymers are suitably block copolymers and are preferably hydrogenated to such an extent that the majority of the olefinic unsaturation is saturated. Many other classes of viscosity modifiers are known in the prior art, and most are described in the Proceedings "Viscosity and Flow Behavior of Multi-Grade Engine Oils" (Esslingen, Germany, December 1977). In addition, it is also known in the prior art that viscosity modifiers can be functionalized in order to introduce dispersibility (for example, block copolymer or polymethacrylate based dispersant viscosity index improvers) and/or or antioxidant functionality and viscosity modification, and they may also have pour point depressants incorporated in order to obtain cold climate processable products. (b) Ashless or ash-containing extreme pressure/antiwear additives, such as metal-containing dithiophosphates or ashless dithiocarbamates, and mixtures thereof. The actual composition of the ingredients will vary depending on the end use and, therefore, can be based on a class of metal ions and various alcohols, where both the alkyl and aromatic moieties can vary in size. Preferred are zinc dithiophosphates (ZDTPs) or sodium dithiophosphates. (c) Dispersants, including succinimides and Mannich bases of various molecular weights and types of amines, including borates (esters), or esters of various types and molecular weights. Preferred are ashless dispersants, such as polyolefin substituted succinimides, for example those described in GB-A-2231873. (d) Antioxidants, such as amine antioxidants, such as "IRGANOX" (trademark) L57 (tertiary C ₄ -C ₁₂ alkyl diphenylamine phenol type such as "IRGANOX" (trademark) L135 (2,6-ditertiary Butyl-4-(2-carboxy(alkyl)ethyl)phenol) (available from CIBA Specialty Chemicals) or soluble copper compounds at copper concentrations between 50-500 ppm. (e) For example, ethylene/propylene embedded (f) Friction modifiers for fuel economy, either metal-containing (purchased from molybdenum) or metal-free esters and amines, or derivatives of these modifiers Synergistic mixtures. (g) Detergents containing metals, such as phenates, sulfonates, salicylates or naphthenates, or mixtures thereof, all of which may be neutral or Overbased, said overbased detergents are carbonates, hydroxides or mixtures thereof. The metal is preferably calcium, magnesium or manganese, but alkali metals such as sodium or potassium may also be used. (h) Copper deactivators, preferably alkylated or benzylated triazoles.

The reaction products of the invention can also be used as additives to fuels, for example as dispersants for soil release additives. Accordingly, the present invention also provides a fuel composition comprising a large amount (greater than 50% by weight) of a base fuel and a small amount (less than 50% by weight), preferably from 0.001-2% by weight, more preferably from 0.001- 0.5% by weight, especially preferred is from 0.002-0.2% by weight (active matter) of the reaction product of the invention, the percentages being all based on the total weight of the composition.

Suitable base fuels include gasoline and diesel fuel. These base fuels may contain saturated, mixtures of olefins and aromatics and may contain, for example, 0.001-0.1% by weight sulfur. They can be derived from straight-run gasoline, synthetically produced aromatic mixtures, hydrocarbon feedstocks from thermal catalytic cracking, hydrocracked petroleum fractions, or catalytically reformed hydrocarbons.

The fuel composition according to the present invention may contain various additives known in the prior art, such as: (a) antiknock additives, such as lead compounds, or other compounds such as tricarbonylmethylcyclopentadienyl manganese or ortho Azidophenylmethylcyclopentadienylmanganese. (b) Co-antiknock agents such as benzoylacetone. (c) Cloud remover, such as the following commercially available products: "NALCO" (trademark) EC5462A (available from Nalco), "TOLAD" (trademark) 2683 (available from Baker Petrolite), EXP177, EXP159M, EXP175, EP409 or EP435 (available from RE Speciality Chemicals), and T9360-K, T9305, T9308, T9311 or T327 (available from Baker Petrolite). (d) Antifoaming agents, such as the following commercially available products: "TEGOPREN" (trademark) 5851, Q25907, MR1027, MR 2068 or MR2057 (available from Dow Corning Corporation), "RHODORSIL" (trademark) (available from Rhone Poulenc), and "WITCO" (trademark) SAGTP325 or SAG327 (available from Witco). (e) Ignition modifiers (for example, 2-ethylhexyl nitrate, cyclohexyl nitrate, di-tert-butyl peroxide and Said substances. (f) Rust inhibitors (such as commercial products sold as "RC 4801" by Rhein Chemie (Mannheim, Germany), or polyol esters of succinic acid derivatives in their α - an unsubstituted or substituted aliphatic hydrocarbon group of from 20 to 500 carbon atoms in at least one position of the carbon atom (eg polyisobutylene substituted pentaerythritol diester of succinic acid). (g) Deodorants.( h) Anti-wear additives. (i) Antioxidants (for example, phenols, such as 2,6-di-tert-butylphenol, or phenylenediamines, such as N, N'-di-sec-butyl-p-benzenediamine Amines). (j) metal deactivators. (k) lubricants, such as the following commercially available products: EC831, "PARADYNE" (trademark) 631 or 655 (available from Paramins) or "VEKTRON" (trademark) 6010 (available from from Shell Additives International Limited). (l) a carrier liquid, such as a polyether, for example C ₁₂ -C ₁₅ alkyl substituted propylene glycol ("SAP 949", "HVI" or "XHVI" (trademark) crude oil, these products are available from Royal Dutch division/Shell group of companies, polyolefins derived from _C2 - _C6 monomers, such as polyisobutenes having 20-175, especially 35-150, carbon atoms; or polyalphaolefins, said Polyalphaolefins have a viscosity at 100°C from 2×10 ^-6 to 2×10 ^-5 m ² /s (2-20 centistokes), and are composed of at least one alpha-olefin containing 8-18 carbon atoms Monomer derived hydrogenated oligomers containing 18-80 carbon atoms.

Lubricating oil compositions and fuel compositions of the present invention can be prepared by adding the substituted or unsubstituted reaction products of the present invention to lubricating crude oils or base fuels. Concentrates of additives are blended with lubricating base oils and base fuels for convenience. Such concentrates generally comprise an inert carrier liquid and one or more additives in concentrated form. Accordingly, the present invention also provides an additive concentrate comprising: an inert carrier liquid and 10-80% by weight (active matter), of the substituted or unsubstituted reaction product of the present invention, wherein the percentages are based on the total weight of the concentrate.

Examples of inert carrier liquids include hydrocarbons, and mixtures of hydrocarbons with alcohols or ethers, such as methanol, ethanol, propanol, 2-butoxyethanol or methyl t-butyl ether. For example, the carrier liquid can be an aromatic hydrocarbon solvent such as toluene, xylene, mixtures thereof or mixtures of toluene or xylene with alcohols. Alternatively, the carrier fluid may be a mineral crude oil or a mixture of mineral crude oils, such as the product sold under the trade name "HVI" by the Royal Dutch Division/Shell Group of Companies, for example "HVI 60" crude oil, or by the Royal Dutch Division/Shell Group of Companies Synthetic hydrocarbon crude oil sold by the Company under the trade name "XHVI" (trademark).

Non-limiting examples of suitable additive concentrations in the final blended lubricating oil composition: Oil component% mass A B C D. E. f Alkaline earth metal sulfonate detergent 3.8 3.4 - - - - Alkaline earth metal phenate detergent 1.2 1.1 - - - - Alkaline earth metal salicylate detergent - - 4.6 2.5 3.6 10.5 high molecular weight dispersant - 5.5 8.0 5.0 11.5 - low molecular weight dispersant 6.0 2.0 - - - 9.0 Master ZDTP 0.5 - - 0.3 - 0.7 sub-ZDTP 0.4 1.0 0.9 0.7 1.2 0.6 Amine antioxidants - - 0.6 0.8 0.3 - Phenolic Antioxidants 0.7 1.2 - - - - crude margin margin margin margin margin margin

Non-limiting examples of suitable additive concentrations for blending lubricating oil compositions: Oil component% mass A B C D. E. f Alkaline earth metal sulfonate detergent 29.9 23.8 - - - - Alkaline earth metal phenate detergent 9.4 7.7 - - - - Alkaline earth metal salicylate detergent - - 32.4 26.6 21.6 50.2 high molecular weight dispersant - 38.5 56.3 53.2 68.9 - low molecular weight dispersant 47.2 14.0 - - - 43.1 Master ZDTP 3.9 - - 3.2 - 3.3 sub-ZDTP 3.1 7.0 6.3 7.4 7.2 2.9 Amine antioxidants - - 4.2 8.5 1.8 - Phenolic Antioxidants 5.5 8.4 - - - - crude margin margin margin margin margin margin

In addition, the present invention also provides the use of the substituted or unsubstituted reaction product of the present invention as a dispersant, detergent or antioxidant additive.

The following examples illustrate the invention. Examples 1-5 are model tests. They use living carbocationic dimerization systems derived from 2-chloro-2,4,4-trimethylpentane (thus analogous to isobutylene dimer), rather than living carbocationic polymerization systems as reactants. Examples 6-10 illustrate the products of the invention using polyisobutene as a polymerization component. Finally, Example 11 concerns the oxidation resistance test of thiophene-functionalized PIBs, an illustrative use of the novel products of the present invention, while Example 12 illustrates the dispersion properties of functionalized PIBs.

Typically, the examples were carried out in batch reactors immersed in an external cooling bath. Thoroughly dry solvents and reactants. The following abbreviations are used in the examples:

CTMP 2-chloro-2,4,4-trimethylpentane

tmb 1,1,3,3-tetramethylbutyl (free radical)

PIB Polyisobutylene or its free radicals

IB isobutylene

MCH Methylcyclohexane

DCM Dichloromethane

MeOH Methanol

TH Thiophene

BrTH 2-Bromothiophene

MeTH 2-Methylthiophene

BTH 2,2'-Dithienyl

DBTH 3-dodecyl-2,2-dithienyl

DTHCE 1,1-bis(2-thienyl)-2,2,2-trichloroethane

FU furan

Me-FU 2-Methylfuran

DtBP 2,6-di-tert-butylpyridine.

synthetic DBTH

DBTH is prepared by the reaction of 3-bromoBTH with dodecylmagnesium bromide. 3-BromoBTH is prepared by the reaction of 2-thiophene magnesium bromide with BrTH in the presence of 1,1'-bis(diphenylphosphino)ferrocene.

Example 1

Into a three necked round bottom flask (250 ml) equipped with a magnetic stirrer, 305 mg (2.05 mmol) CTMP was added, followed by 40 ml 60:40 v/v MCH/DCM and 1385 mg (10.02 mmol) cis-decalin (decaline) (intra mark). The reactor was then cooled to -80°C and then 1869 mg (9.85 mmol) of TiCl ₄ dissolved in 40 ml MCH/DCM was added. Next, 90 mg (1.07 mmol) TH dissolved in 20 ml MCH/DCM was added. Samples of 2 ml were then withdrawn at intervals and quenched with MeOH at -80°C and analyzed by gas-liquid chromatography.

GLC shows the degree of conversion and ratio between capped and coupled products, 2-(tmb)TH(I) and 2,5-bis(tmb)TH(II). After 2 hours, the degree of conversion reached 60% (at the inlet TH) and the product ratio I/II was 83/17. After stirring overnight, the mixture was allowed to warm to room temperature and at a ratio of 54/36 97.4% conversion was achieved.

Example 2

Under the same conditions as in Example 1, when 1.28 g (10 mmol) of 2-acetyl TH was used instead of TH, no reaction occurred. Clearly, the 2-acetyl group is a passivating group.

Example 3

Under the same conditions as in Example 1, when TH was replaced by 0.82 g (10 mmol) Me-FU, 1.32 g of 2-methyl-5(tmb)FU was produced within half an hour. The following analytical data were obtained: ¹ H-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); ¹³ C-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.

Example 4

To a three-neck round bottom flask (250ml) equipped with a magnetic stirrer, 7.55g (51mmol) of CTMP was added followed by 5.0g (51mmol) of MeTH dissolved in 20ml of DCM. 0.870 g (6.13 mmol) BF ₃ OEt ₂ was added slowly and the reaction was analyzed by GLC. According to the GLC data, a monoalkylated product with a small amount of dialkylated product formed immediately after the addition of the Lewis acid was formed.

The crude product is washed, dried and partially distilled (kugelrohr). It was found that 19% of MeTH was converted to 2-methyl-5(tmb)TH.

Example 5

According to the procedure of Example 1, using 0.555g (3.75mmol) CTMP dissolved in 10ml 40:60v/v hexane:DCM; 3.55g (18.75mmol) _TiCl4 dissolved in 20ml of said solvent; and 0.60g ( 1.875 mmol) was dissolved in 20 ml of DBTH in said solvent. The progress of the reaction was determined by GC where two independent peaks of the same size were found and the relationship of 5-(tmb)DBTH and 5'-(tmb)DBTH was shown (by GC-MS). A conversion of 75% was achieved.

Example 6

PIB-functionalization experiments were performed using TH, BrTH, MeTH, DTHCE, DBTH, FU, and MeFU.

Polymerization _of isobutene was carried out by a simple laboratory polymerization procedure at -78°C by using a _CH2Cl2 /hexane solvent mixture. After reaching a high (about 100%) monomer conversion, the aromatic ring system is added. Changes in chain end structure were detected during the GPC run by UV spectroscopic detection as well as ^by1H NMR spectroscopy.

The experimental conditions for capping with BrTH were as follows: The reactor was charged with 6.2 mmol of CTMP, 5.2 mmol of 2,2'dipyridyl, 150 ml _{of CH2Cl2} and 350 ml of hexane. The solution was cooled to -78°C, then 5ml IB was added, and 100ml _TiCl4 dissolved in _CH2Cl2 ( _0.18M ). After 5 minutes and 10 minutes, another 4ml of IB was added. When the polymerization was complete, 31 mmol of BrTH dissolved in 100 ml (pre-cooled) _CH2Cl2 was added to the reaction mixture and the reaction _was monitored occasionally (using pre-cooled methanol as quench).

The experimental conditions for capping with MeTH were as follows: The reactor was charged with 3.6 mmol of CTMP, 2.4 mmol of 2,2'dipyridyl, 50 ml _{of CH2Cl2} and 140 ml of hexane. The solution was cooled to -78°C, then 5ml IB was added, and 50ml _TiCl4 dissolved in _CH2Cl2 ( _0.24M ). After 5 and 10 minutes, another 5 ml of IB was added. When the polymerization was complete, 10 mmol of MeTH dissolved in 50 ml (pre-cooled) _CH2Cl2 was added to the _reaction mixture and the reaction was monitored occasionally (using pre-cooled methanol as quench).

Both BrTH and MeTH will quantitatively convert polyisobutylene (PIB) chain ends to the corresponding heterocyclic functionality. The reaction between the carbocation chain ends and these compounds is a fairly rapid process; UV analysis indicated that the quantitative conversion would take place within 30-45 min with BrTH and correspondingly in 10-20 min with MeTH.

¹ H NMR spectrum showed the following signals: for 2-bromo-thiophene at 6.55 (d, 2H), 6.80 (d, 2H); for 2-methyl-thiophene, at 6.50 (d, 2H), 6.55 (d , 2H), the spectra indicated that the corresponding chain ends were formed upon functionalization with BrTH and MeTH, respectively. Notably, for heterocyclic chain ends, an aromatic signal will be displayed, whereas -CH ₂ - groups for tertiary chlorine chain ends in PIBs quenched with nucleophiles that do not react with cationic chain ends characterize , without any signal at 1.94ppm. Spectroscopic results (UV and NMR) indicated quantitative end quenching with BrTH and MeTH.

Coupling of living PIB chains was also attempted via dithienyl groups. The UV signal by GPC indicated efficient addition of the dithienyl group to the chain end. However, its molecular weight is consistent with neither DBTH nor DTHCE induced chain coupling. In the presence of DBTH, heating the polymerization system to room temperature will not cause coupling.

It was also found through previous experiments that furan and 2-methylfuran would also react with the active PIB chains.

Example 7

Isobutylene polymerization was carried out at -78°C using 33 mmol CTMP, 49 mmol DtBP and 131 mmol _TiCl4 as starting system; 600 ml 60:40 v/v MCH/DCM as solvent and 1114 mmol IB. After 1 hour, 31 mmol MeTH was added. Quantitative conversion to 2-methyl-5(PIB)TH was found within 30 minutes.

Example 8

Isobutylene polymerization was carried out at -78°C using 16.5 mmol CTMP, 4.2 mmol DtBP and 63 mmol _TiCl4 as starting system; 600 ml 60:40 v/v MCH/DCM as solvent and 604 mmol IB. The number average molecular weight of the polymer formed was 2244. After 1 hour, 7.3 mmol TH were added. It was found that quantitative conversion would occur within 30 minutes. The products were assayed to contain 2-(PIB)TH (Mn of 2575) and 2-5-bis(PIB)TH (Mn of 3121).

Example 9

Isobutylene polymerization was carried out at -78°C using 16.8 mmol CTMP, 24 mmol DtBP and 65 mmol _TiCl4 as starting system; 600 ml 60:40 v/v MCH/DCM as solvent and 566 mmol IB. After 0.5 h, 21 mmol MeFU was added. Quantitative conversion to 2-methyl-5(PIB)FU was found within 30 minutes.

Example 10

Isobutene polymerization was carried out at -78°C using 60 mmol CTMP, 30.1 mmol 2,2'-dipyridyl and 562.5 mmol _TiCl4 as starting system; 1200 ml 60:40 v/v MCH/DCM as solvent and 916 mmol IB. After 1 hour, 50% of the solution was removed. To the remaining solution was added 60 mmol ethyl-2-thiophene acetate. After 2 hours, GPC, ¹ H and ¹³ C-NMR confirmed the presence of the desired functionalized PIB.

Example 11

Utilize isothermal differential scanning calorimetry (DSC) analysis method, make the fully prepared oil (comprising dispersant, detergent, zinc dithiophosphate as extreme pressure antiwear agent, and 1% by weight, Mn respectively 1500 and 3500, 2-methylthienyl-terminated PIB) were subjected to the antioxidant test.

The analyzes were performed using two Mettler-Toledo instruments (DSC27HP). Therefore, 2.00 ± 0.05 mg sample was placed in an aluminum pan and loaded into the DSC unit. Then, using a Brooks pressure and mass flow controller, the oxygen pressure and flow rate were set to 3.4 MPa (500 psig) and 60 standard ml/min. The sample is rapidly heated to the test temperature of 200°C by overriding the rate control. Then, monitor the power output while maintaining the sample at the test temperature. The induction period was measured by taking the intercept of the baseline at the point of maximum slope on the rising side of the exothermic peak identified by taking the derivative of the enthalpy profile from the baseline.

This test showed an average induction period of 13.7 and 13.6 minutes for the samples, respectively, compared to an average induction period of 10.9 minutes for the PIB formulated oil without 2-methylthienyl capping.

In other words, these 2-methylthienyl-terminated PIBs are effective antioxidants.

Example 12

The product of Example 10 (Mn=3180; 3.0mmol) and N,N-dimethyl-1,3-diaminopropane (DAP; 150mmol) were placed in a three-necked flask equipped with a reflux condenser, and Heating at 130°C for 10 hours. Excess DAP was removed under vacuum. The resulting reaction mixture was diluted with hexane (60ml) and washed with methanol (3 x 30ml). The organic layer was dried over _MgSO4 and filtered. Removal of the solvent leaves a highly viscous material. Yield: 75%.

¹³ C-NMR: Clear signals of bonded thienyl groups and bonded DAP carbons appeared at 170.1, 157.7, 133.4, 126.5 and 122.2 ppm, and 58.8, 58.4 and 45.3 ppm, respectively.

IR: At 1660cm ^-1 there is a clear signal of amide carbonyl, no ester carbonyl.

Elemental analysis: 1.07% by weight N, 0.90% by weight S.

The product of Example 12 was subjected to a dispersibility test by way of its viscometry using a Bohlin VOR (Viscometry-Oscillation-Relaxation) rheometer. Samples (25 grams) were incorporated into HVI-65 NS crude oil at 60-85°C using a hot plate and magnetic stir bar. The active substance content is 2% by weight. Weigh 1.25 grams of carbon black (Cabot Vulcan XC72R) into a 150 ml Schott bottle and pour the hot mix oil using a paddle over the carbon black and allow to drain. The bottle was capped and conveyed to a heated stirring device set at 100°C where it was brought to thermal equilibrium and stirred. The hot sample is then poured into the hot cup of the rheometer geometry, and it is determined by comparison with a reference sample that contains carbon at a shear rate of 0.2 ^s The viscosity of the black formulation was reduced by 66%.

In other words, these functionalized PIBs are effective dispersants.

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.