JP2001504893A - Functional polymer - Google Patents

Abstract

  (57) [Summary] A method for functionalizing a polymer synthesized by carbocationic polymerization in which a living carbocationic polymerization system reacts with one or more aromatic ring systems, and lubricating oils or fuel compositions and additive concentrates, such as dispersants, Use of substituted or unsubstituted reaction products by the above method as detergent or antioxidant additive or VI improver.

Description

DETAILED DESCRIPTION OF THE INVENTION                             Functional polymer   The present invention provides a novel polymer that functions by carbocationic polymerization. Methods and novel functional polymers such as telechelic prepolymers .   Polymers with functional groups may be lubricating additives, compatibles, emulsifiers or It is useful as a raw material for manufacturing adhesives, improvers, coating materials, sealing materials, etc. You. Therefore, functional polymers are of great interest.   Carbocationic polymerization is one of the known synthetic polymer synthetic routes. example WO-A-94 / 13706, for example, describes a new polymeric material, ribbed, functionalized with nitrogen-containing functional groups. Discloses a method of direct synthesis by cationic polymerization. Polymerization and functionalization Occur in essentially the same manner (eg, a one-step Friedel-Crafts reaction). Subject "Polymers Designed by Carbocation Macromolecular Engineering: Science Theory and Practice '' (Hanser, 1991), in section II.5.2, author J.P. Many additional terminal groups are present in both fins and poly (alkyl vinyl ethers). Many examples are given.   One-stage carbocation heavy with novel terminal groups that may react further It will be appreciated that an integrated process is highly desired.   Thus, a living carbocationic polymerization system reacts with one or more aromatic ring systems. Finding ways to functionalize polymers synthesized by bocationic polymerization Was.   This method is particularly useful if one or two of the aromatic ring systems is a heterocyclic ring of 5-, 6-, or 7-atoms. This is suitable for the case where a selection is made. Such heterocycles include N, O, P, and S Having one or more heteroatoms selected from Provides the electron rich environment required for the Le-Crafts reaction to occur. 1 or more Is preferably selected from 6-π-electron ring systems. Especially preferred Aromatic ring systems include pyrrole, furan, thiophene, oxazole, isothia Examples include sol, 1,3,4-thiadiazole, and pyrazole.   These aromatic ring systems do not sterically hinder the remaining reactive portion of the aromatic ring system, If the aromatic ring system is not deactivated, it may be partially substituted. For example, replace The group is amino, hydroxy, alkoxy, aminocarbonyl, alkyl or ally Or a halogen group. The first mentioned substituents are strong Is an active group. Such substituents include, for example, aromatic ring systems as coupling agents. When acting on a relatively large basis, the first substituent is (on average) the functional polymer. T) corresponding to half the molecular weight. Examples of suitable substituted aromatic rings include, for example, 3,3-di There are methyl-3H-pyrazole and 2,2-bithienyl.   Also, one or more aromatic ring systems include naphthalene, quinoline, quinoxaline, , Benzofurans, benzothiophenes, pteridine, purines, indolizines And (benzo-) fused ring systems such as In addition, one or more of these May be partially substituted with the same substituents described above.   One or more aromatic ring systems include pyrrole, furan, thiophene and their derivatives. Preferably it is selected from the body. The polymer synthesized in this way is pyrrole With the well-known and very extensive chemistry of the structures of Will be further functionalized. The use of thiophenes or substituted thiophenes The advantage is the inherent antioxidant properties of the functional polymer.   As used throughout this specification, the definition of living polymer is defined above. I want to. Living carbocationic polymerization system is a cation without chain transfer and termination reaction Living Polymerization Based on Sexual Initiation and Fast Reversible Chain Transfer and / or Termination Reactions exist and the speed of these processes is faster than the speed of the growth reaction And polymerization. That is, the system is capable of irreversible chain transfer and / or termination reactions. The degree is zero or appears to be zero.   As stated in the textbook, (living) carbocationic polymers are: A controlled initiation reaction, i.e., a monofunctional or multifunctional initiator, The mer chain is controlled to grow in one direction at one end or in multiple directions, at the center. Generated by the starting reaction.   Suitable living carbocationic polymerization systems include, for example, t-alkyl esters / BCl_Three; Cumyl acetate / TiCl_Four; 2,2'-bipyridyl / TiCl_Four; CH_ThreeSO_FourH / SnCl_Four + N-Bu_FourNCl; HI / I_TwoHI / ZnX_TwoOr SnX_Two(X = Cl, Br); HI / ZnI_Two; Or CH_ThreeCOCIO_FourBut, As each monomer, for example, isobutene; isobutene / 2,4-dimethyl-1 1,3-pentadiene; styrene; p-vinylphenyl glycidyl ether; Vinyl ether; methyl vinyl ether / p-methoxystyrene; or 2-methyl There is dihydrofuran (a more comprehensive list can be found in Table I on pages 43-55 of the textbook above) V). Further, in WO-A-94 / 13706, nitrogen-containing compounds used as initiators are used. Compounds such as diethylaluminum chloride, TiCl_FourOr BCI_ThreeMixed with 2-azido-isopropyl-benzene or bis (2-azido-isopropyl) benzene May be used.   Although an insoluble catalyst may be used, a homogeneous catalyst is preferably used. In the polymerization method It is common to use a solvent. The preferred freezing point of the solvent is Below the degree (pretty much). Specifically, but not exclusively, C_Two~ C_TenA Lucane, -Alkene, -Alkyl are liability and -Alkenyl halide, Carbon tetrachloride , Carbon disulfide, nitroethane, liquid carbonic acid and methylchlorohexane . Preferred solvents are low boiling alkyl halides: chloroform, methylene dichloride , Methyl chloride, ethyl chloride, propyl chloride, n-butyl chloride, and 1,2-dichloroethyl And neopentane, hexane, heptane, and refined petroleum ether.   Any cationically polymerizable monomer may be used, and linear and branched alpha -Olefin, isoolefin, alicyclic monoolefin, alicyclic compound, polystyrene Derivatives, indene and its derivatives, and other monoolefins, and Kennedy's Textbook "Cationic Polymerization of Olefins: Critical Inventory; Pages 39-53 (Wiley, 1975)" Includes cationic polymerizable polymers of the identified heterocycles. Use vinyl ether Wear.   Particularly useful polymers are isoolefins of 4 to 20 carbon atoms or mixtures thereof. Can be synthesized from compounds. Such unsaturated hydrocarbons are not limited But not isobutene, 2-methyl-butene, 3-methyl-1-butene, 4-methyl-1-pen Ten, and beta-pinene. Other available cationically polymerizable monomers -Addition to heterocyclic monomers such as oxazoline, and polar covalent bonds You There is a well-known thing. If necessary, the mixture of cationically polymerizable monomers may be polymerized. It can be used as a feed for the zone. Thus, copolymer, terpo Limers and higher interpolymers can be mixed with two, three or more monomers It can be synthesized using an object. The preferred feed to the polymerization zone is pure isobutene And C_FourMixed C resulting from pyrolysis or catalytic cracking of hydrocarbons such as naphtha_Four Contains hydrocarbon fractions. A suitable isobutene feed is typically at least 10%, It contains up to 100% by weight of isobutane, based on the weight of the feed. Industrial C suitable for use as an important feedstock_FourThe fraction is 10-40% 1-butene , 10-40% 2-butene, 40-60% isobutane, 4-10% n-butane, and 0.5% Up to butadiene. Where all percentages are percentages by weight relative to the weight supplied. Rate. Also, the feedstock containing isobutene may be present in small amounts, e.g. %, Preferably less than 10%, most preferably less than 5% of propadiene, Lopylene and C_FiveC, such as an olefin_FourOther polymerizable olefin monomers May be contained. As used herein, the term "polyisobutene" refers to isobutene. Not only homopolymers but also copolymers of isobutene and the usual C_FourAlong with the distillate, Usually a C containing 3-6, preferably 3-5 carbon atoms_FourNot ethylenically unsaturated Also intended to include refining monomers, such copolymers are Usually at least 50% by weight relative to the number average molecular weight (Mn), preferably at least Provided it contains 65%, and most preferably at least 80%, of isobutene units I do. Under the conditions specified here, isobutene polymerizes very selectively, The amount of isobutene described above can be minimized.   Preferably, the solvent of the polymerization does not essentially inhibit the catalyst. For example, Olefy The feed is treated using a molecular sieve, washed with caustic, e.g., mercaptan, water , And diene (if necessary).   The polymerization reaction is carried out batchwise or continuously by supplying the materials to the reactor, slurry or (Semi) continuous removal of polymer solution overflow for polymer regeneration Can be done by operation. From the viewpoint of operability, a preferable reaction method is that the raw materials are continuous. Continuous flow stirred reactor where the product is fed to the reactor and the product is removed from the reactor This is a method based on continuity using. However, a more limited range (narrower In the case of the (quantity distribution), a batch method is preferable.   The amount of the catalyst used in the method of the present invention depends on the target polymer number average molecular weight. Can be changed as follows. Also, by changing the amount of catalyst, No isomerization can be minimized or reduced. If the concentration of the initiator in the reaction layer is The lower, the higher the molecular weight of the polymer, and vice versa. The selected goal Control of polymer molecular weight within a defined range of polymer molecular weights Of particular importance when intended for use in lubricating oils as dispersants. The amount of catalyst also affects olefin monomer conversion and polymer yield, Larger amounts of medium usually lead to higher conversions and yields. Using a sufficient amount of catalyst, The reaction should be a "living" cationic polymerization.   Performing the polymerization reaction in the liquid phase leads to linear or chain type polymerization without cyclization or branching. Wake up. When using gaseous raw materials under ambient conditions, keep the raw materials in the liquid phase Control the reaction pressure and / or dilute the raw material with an inert solvent or liquid It is preferable to dissolve in the agent. The catalyst selected under normal conditions is a gas (eg, BF_Three Etc.), the gaseous catalyst is usually added partially or entirely to the reactor and then added. Dissolves in pressurized liquid. The polymerization pressure is usually in the range of 25 to 500, preferably 100 to 300 kPa It is.   If the reaction temperature is too high, the degree of functionalization tends to decrease, and The temperature performed is important. Normal polymerization temperature range is between -100 ℃ and + 10 ℃ . -10 ° C or lower, preferably -20 ° C or lower, and between -80 ° C and -20 ° C, for example, at -50 ° C. Preferably, polymerization is performed. The temperature of the liquid phase reaction mixture can be Controlled. Select a specific reaction temperature to achieve the target living polymerization and select it It is preferred that the temperature does not change by more than + or -5 ° C. Meanwhile, the catalyst And / or the feed rate of the accelerator is varied to achieve the desired Mn to achieve the desired Mn in the starting composition. It is preferable to compensate for the change in the nomer distribution.   The average polymerization time can vary from 10 to 120 minutes, preferably from 15 to 4 minutes. 5 minutes, more preferably 15 to 30 minutes, most preferably 15 to 20 minutes.   The reaction, the Friedel-Crafts alkylation reaction, is a carbocationic polymerization. Occurs under the same conditions required to form the system. Therefore, these conditions are It is well known to those skilled in the art. In addition, Friedel-Crafts alkyl The reaction is well known and examples of suitable conditions, and further references, are described, for example, in J. Marc h, "Higher Organic Chemistry" (3rd edition, sections 1-13, 1985). Typical conditions Is a method of controlling temperature to remove heat of reaction, solvent and contacting reagent (Including stirrers).   The materials used to quench the reaction are conventional and deactivate the catalyst Although an excess amount is used in an amount sufficient for the polymerization, usually a cationic polymerization accelerator (for example, (E.g., water, alcohol). Therefore, catalyst deactivation Any amount of quench solvent may be used as long as it is effective for Such an effective amount is sufficient when the molar ratio of quench solvent to catalyst is typically 1: 1 to 100. : 1, preferably 3: 1 to 50: 1, most preferably 10: 1 to 30: 1. Quenching is performed by introducing a quench solvent into the polymer product. Typically, the polymer product is quenched with a gaseous catalyst (if one is used). G) and maintained under sufficient pressure to prevent the other components of the mixture from evaporating Have been. The temperature of the quench solvent is not critical, for example at room temperature or below. Good. In a batch system, quenching takes place in the reactor or the product reacts. It is preferred to work on the product after it has been removed from the vessel. In continuous systems, Quenching is usually performed after the product has been removed from the reactor. After quench The polymerization product is usually processed according to conventional final steps. It is the catalyst residue Caustic / water wash, deactivate and extract the extracted catalyst in aqueous phase A hydrocarbon / aqueous phase separation step, a water washing step to remove residual amounts of neutralized catalyst Including. Then, the polymer is usually stripped in the debutanizer to remove unreacted volatile The light-terminated polymer (e.g., C_{twenty four}Carbon polymer). And usually, the stripped polymer is_Two Dry with.   In theory, the living carbocationic polymerization system exhausted the monomer supply In some cases, a more limited product is synthesized, but during carbocationic polymerization-based synthesis One or more ring systems may be introduced. Living to the amount of one or more aromatic ring systems Depending on the ratio of the carbocationic polymerization system and the functionality of the initiation reaction system, the polymer Is Whether it has a functional end group at one end of the polymer chain (1: 1; monofunctional), one or more ribs Have one or more aromatic ring systems associated with the carbocationic polymerization system (e.g., 2 A so-called branched or star-branched polymer synthesized in a ratio of 1 or more; monofunctional), Living-carbothios end-capped at some or each of the growing ends Polymerized system (so-called telechelic polymer, eg 2: 1 ratio; Or 3: 1 ratio; trifunctional) synthesized and using multifunctional initiators One or more aromatic ring systems act as both coupling agents and functional end groups Even mixed systems are synthesized. Examples include, but are not limited to: I-P-Ar I-P-Ar- (P-I) n Ar-P-I '-(P-Ar) m Ar--P-I "-P-Ar-P-I" -P-Ar Where Ar represents one or more aromatic ring systems and P represents a polymer (eg, homopoly I, indicates a multi-functional initiator, I "indicates a bifunctional initiator, and n and m are each one or more aromatic ring systems or multiples. Shows the number of functional initiators.   A telechelic prepolymer capped with one or more functional end groups, and one or more Branched or star-branched polymers linked by the above multifunctional coupling groups are preferred. New Here, the terminal group and the multifunctional coupling group are a 5-atom, 6-π-electron. It is a heterocycle of the child. The branched or star-branched polymer has one or more functional end groups. Preferably, it is capped with. Here, the terminal group is a 5-atom, 6-π-electron Is a heterocycle.   Telechelic prepolymers and branched or star-branched polymers, especially one or more machines Those capped with functional end groups are highly polymerized containing network and VI (viscosity) improvers. Beneficial for the synthesis of quantum products.   The substituted or unsubstituted reaction products of the present invention can be used together with VI improvers, for example in lubricating oils. It can be used as an added dispersant or antioxidant. Therefore, the present invention (50% w or more) lubricant base oil and a small amount (less than 50% w), preferably 0.1-20% w, especially 0.5-10% w (active substance) substituted or unsubstituted reaction products of the invention The present invention provides a lubricating oil composition comprising: Here, the percentage is based on the total weight of the composition. Weight percent relative to   Lubricating formulations are synthesized by adding an additive package to a lubricating oil. Small amount of viscosity change A benign may be included if the final lubricating formulation is a multi-grade version. Made The type and amount of additive package used in the vehicle Gin, ship and rail diesel engine, gas engine, steady power engine and End use, including spark ignition engines and compression ignition engines, including turbines and turbines It depends on the way.   Lubricating formulations are available from the American Automotive Industry Association (SAE), the American Petroleum Institute (API), and American Meet a set of performance specifications classified by the Rica Test Materials Association (ASTM) tripartite coordination It is blended as follows. In addition, an organization called the International Lubricant Standards Approval Committee (ILSA) The American Automobile Manufacturers Association (AAMA) and the Japan Automobile Manufacturers Association (JAMA) Similarly, gasoline-the lowest performance standard for engine oil fueling passenger cars Has been created.   In Europe, the classification of engine oils is based on the ) And the European Lubricant Industry Association (ATIEL) Association (ACEA). Classification system for these internationally organized oils In addition to many, but not all, original equipment manufacturers (OEMs), (I.e., the factory), the performance requirements of the company that must be met with the lubrication formulation used throughout. Have a case.   Suitable lubricating base oils are natural, mineral or synthetic lubricating oils.   Natural lubricating oils include animal oils and vegetable oils such as castor oil. mineral oil Is a lubricating oil fraction obtained from crude oil, for example, naphthalene or paraffinic or The mixture contains coal or shale, and the fraction is clay-acid, solvent, or hydrogenated It can be subjected to a specific process, such as a process. Synthetic lubricating oils are Are known, for example, polymer alpha olefins, isomerized slack wax, Hydrocarbon synthetic poly derived from synthetic alkylene oxide polymers and esters Including mer. These lubricants are used in crankcases for spark ignition and compression ignition engines. Oil lubricant products are preferred, but hydraulic lubricants, metal-working fluids and trucks It also includes a transmission fluid.   The lubricant base oil of the composition of the present invention may be a mineral lubricating oil or Royal Dutch / Shell A mixture of mineral lubricating oils sold under the trademark "HVI" by a group company, or R Synthetic carbonization sold under the trademark "XHVI" by a company of the oyal Dutch / Shell group Hydrogen-based oils are preferred.   The viscosity of the lubricant base oil present in the composition of the present invention can vary widely, Usually, at 100 ° C., it is 3 to 35 mm2 / s.   The lubricating oil of the present invention may include various other additives known in the art. For example ,As follows.   (a) viscosity improvers or regulators; Viscosity improvers can be solid or natural or synthetic It can be a concentrate in the base oil and can be defined as a substance, usually a polymer, Incorporate to essentially improve viscosity (eg, ASTM procedure D2270) (eg, If at least 5 units). All of these are incorporated into the final lubrication formulation Can have desired characteristics. Examples of such viscosity improvers include isop Linear or star polymers of dienes such as butene or butadiene, or optionally There are copolymers of such dienes with substituted styrene. These copolymers -Is preferably a block copolymer, in which most of the olefinic unsaturation is saturated. It is preferable that the hydrogenation is performed to some extent. Many of the other types of viscosity improvers Known in the art, many of them are referred to as "viscosity of multi-grade engine oils. And flow characteristics "(Esslingen, Germany, December 1977) You. Further, a viscosity improver functions as a dispersant (for example, a block copolymer). Dispersant based on limmer or polymethacrylate), and / or It is known that it is functional as an antioxidant together with the improvement. Pour point depressants can be mixed to give products that are easier to handle in cold weather. Wear.   (b) metals containing, for example, ashless or ash-dithiocarbamate systems, and mixtures thereof Ashless or ash containing overpressure / antiwear additives, such as Each configuration The exact composition will depend on the end use and, therefore, the type and variety of metal ions. Range of alcohols and the size of both alkyl and aryl moieties Based on such range. Preferably, zinc dithiophosphates (ZDTPs) or sodium Umdithiophosphate.   (c) ester succinimides and Mannich bases, various molecular weights and borates Includes amine-based, including variants due to, or esters of various types and molecular weights Dispersant. Polyolefin-substituted succinimides, such as those described in GB-A-2231873 Ashless dispersants such as those are preferred.   (d) For example, "IRGANOX" (registered trademark) L57 (Tertiary C_Four-C₁₂Alkyl diphenylamido Amines such as (I) or "IRGANOX" (registered trademark) L135 (2,6-ditert-butyl- 4- (2-carboxy (alkyl) ethyl) phenol) (for example, CIBA Specialty Che micals) or soluble copper compounds with a copper concentration of 50-500 ppm Antioxidant that is a thing.   (e) For example, an ethylene / propylene block copolymer-based rust preventive compound.   (f) Friction modifiers for fuel economy. Contains or contains metal (eg, molybdenum) Esters and amines, or synthetic mixtures thereof.   (g) phenate, sulfonate, salicylate, or naphthenate, or Metal-containing detergents, such as mixtures thereof. All detergents are neutral or Detergents that are either basic or more, such carbonates are carbonates , Hydroxide, or a mixture thereof. Metal is sodium or potassium Alkali metals such as calcium, magnesium, or manganese can be used. preferable.   (h) Copper passivators, preferably alkylated or benzylated triazoles.   In addition, the reaction product of the present invention can be used as, for example, a dispersant for a detergent. It can also be used as an additive in ingredients. Therefore, the present invention provides a method for preparing a major amount (50% w or more) And a small amount (less than 50% w), preferably 0.001-5% w, especially 0.001 w Also provided is a fuel composition containing 反 応 2% w (active material) of the reaction product of the present invention. Here, the weight percentage is based on the total weight of the composition.   Suitable base fuels include gasoline and diesel fuel. These base fuels May comprise a mixture of saturated olefins and aromatic hydrocarbons, e.g., 0.1. Sulfur may be contained in the range of 001 to 01.% w. They are straight-run gasoline, synthetic Aromatic hydrocarbon mixture, pyrolysis of hydrocarbon feedstock, hydrocracked crude oil fraction, or catalyst From modified hydrocarbons.   The fuel composition of the present invention may include various other additives known in the art. . For example:   (a) An anti-knocking agent. Lead compound or methylcyclopentadienyl-manganese Other compounds, such as tricarbonyl or orthoazidophenyl.   (b) Co-knock inhibitors such as benzoylacetone.   (c) `` NALCO '' (registered trademark) EC5462A (for example, Nalco), `` TOLAD '' (registered trademark) 2683 ( For example, Baker Petrolite), EXP177, EXP159M, EXP175, EP409 or EP435 (e.g. , RE Speciahty Chemicals) and T9360-K, T9305, T9308, T9311 or T327 (eg Commercially available antifoggants such as, for example, Baker Petrolite).   (d) "TEGOPREN" (registered trademark) 5851, Q25907, MR1027, MR2068 or MR2057 (for example, For example, Dow Corning), "PHODORSIL" (registered trademark) (e.g., Rhone Poulenc), and " Commercially available, such as WITCO® SAG TP325 or SAG327 (eg, witco) Defoamer.   (e) an ignition improver (e.g., 2-ethylhexyl nitrate, cyclohexyl nitrate, di-ter t-butyl peroxide, and US-A-4208190, column 2, line 27 to column 3, line 21 Disclosed to the eye).   (f) Rust inhibitors (e.g., Rhein Chemie, Mannheim, `` RC 4801 '' in Germany, or Polyhydric polyhydric alcohol esters of succinic acid derivatives, at least one Unsubstituted or substituted aliphatic hydrocarbons having 20 to 500 carbon atoms on the rufa carbon atom Group-containing succinic acid derivatives (e.g., pentaerythrene of polyisobutylene-substituted succinic acid) Thritol diester)).   (g) Perfume.   (h) antiwear additives.   (i) antioxidants (e.g., phenols such as 2,6-di-tert-butylphenol Or a phenylenediamine such as N, N'-di-sec-butyl-p-phenylenediamine Kind).   (k) EC831, "PARADYNE" (registered trademark) 631 or 655 (for example, Paramins) or "VE KTRON ”(registered trademark) 6010 (for example, Shell Additives International Limited) Such commercially available lubricants.   (1) For example, C<sub>12</sub>~ C<sub>Fifteen</sub>Alkyl-substituted propylene glycol ("SAP 949") Una polyether, "HVI", which is commercially available from a company in the Royal Dutch / Shell group "Or" XHVI "(registered trademark) base oil, C<sub>Two</sub>~ C<sub>6</sub>Poly derived from monomers Olefins, for example polyisobutylene having 20 to 175, especially 35 to 150, carbon atoms Or the viscosity at 100 ° C is 2 × 10<sup>-6</sup>~ 2 × 10<sup>-Five</sup>m<sup>Two</sup>/ s (2-20 centistokes) Derived from at least one alpha olefin having from 8 to 18 carbon atoms Polyalphaolefins are hydrogenated oligomers having 18 to 80 carbon atoms Carrier liquid like.   The lubricating oils and fuel compositions of the present invention lubricate the substituted or unsubstituted reaction products of the present invention. It can be prepared by adding to base oil or base fuel. Capital Suitably, the additive concentrate is mixed with a lubricating base oil or base fuel. this Such concentrates usually contain an inert carrier liquid and a high concentration of one or more additives. In. Therefore, the present invention relates to the use of an inert carrier liquid with 10-80% w (active substance) Also provided is an additive concentrate comprising the substituted or unsubstituted reaction product of the present invention. This Here, the weight percentage is based on the total weight of the concentrate.   Examples of inert carrier liquids include hydrocarbons and methanol, ethanol, Alcohols such as panol, 2-butoxyethanol or methyl tert-butyl ether There are mixtures of hydrocarbons with coals or ethers. For example, carrier The liquid is toluene, xylene, a mixture thereof, or toluene containing alcohol. Or an aromatic hydrocarbon solvent such as a mixture of xylenes. instead of, The carrier liquid may be mineral base oil or from Royal Dutch / Shell Group companies , "HVI", such as those commercially available as "HVI 60" base oils, or R Commercially available as `` XHVI '' (registered trademark) from a company in the oyal Dutch / Shell group. A mixture of such mineral base oils may be used. Non-limiting examples of suitable additive concentrations in the final mixed lubricating oil composition Non-limiting examples of suitable additive concentrates for mixed lubricating oil compositions  In addition, the present invention provides the invention as a dispersant, detergent, antioxidant, or VI improver. The present invention provides for the use of substituted or unsubstituted reaction products.   The following examples illustrate the invention.   Examples 1 to 5 show model experiments. These are living carbokers as reagents. Instead of an on-polymerization system, 2-chloro-2,4,4-triol, similar to a dimer of isobutene Uses a living carbocation dimerization system derived from methylpentane . Examples 6-10 show products of the invention using polyisobutene as the polymer component Illustrate. Finally, Example 11 shows the thiophene-system for the new product of the invention. For the antioxidant test of functional PIB, Example 12 shows the dispersant properties of functional PIBs.   Typically, this example was operated in a batch reactor immersed in an external cooling bath. All solvents and reagents were thoroughly dried. In this embodiment, the following abbreviations are used. You. CTMP 2-chloro-2,4,4-trimethylpentane tmb 1,1,3,3-tetramethylbutyl (radical) PIB polyisobutylene or its radical IB isobutene MCH methylcyclohexane DCM dichloromethane MeOH methanol TH thiophene BrTH 2-bromothiophene MeTH 2-methylthiophene BTH 2,2-bithienyl DBTH 3-Dodecyl-2,2-bithienyl DTHCE 1,1-di (2-thienyl) -2,2,2-trichloroethane FU franc Me-FU 2-methylfuran DtBP 2,6-di-tert-butylpyridineDBTH Synthesis of   DBTH is prepared by the reaction of 3-bromo BTH with dodecyl magnesium bromide. Made. 3-bromoBTH is the presence of 1,1'-bis (diphenylphosphino) ferrocene Below, it was prepared by the reaction of 2-thiophene magnesium bromide with BrTH.Example 1   In a 250 ml three-necked round bottom flask equipped with a magnetic stirrer, 305 mg (2.05 mmo l) of CTMP, then 40 ml of 60:40 v / v MCH / DCM and 1385 mg (10.02 mmol) of Su-decalin was added (internal standard). Then cool the reactor to -80 ° C and add 40ml 1869 mg (9.85 mmol) TiCl dissolved in MCH / DCM_FourWas added. Next, 20 ml of MCH / DCM Was dissolved in 90 mg (1.07 mmol) of TH. Occasionally take a 2 ml sample and place it at -80 ° C for 2m Quenched with 1 MeOH and analyzed by gas liquid chromatography.   GLC shows the degree of conversion and end-capped and coupled products, 2- (tmb) TH (I) and 2,5-bis ( tmb) The ratio of TH (II) was clarified. After 2 hours, the degree of conversion is 60% (based on the intake TH), The product ratio I / II reached 83/17. After stirring overnight, the mixture was warmed to room temperature, At a rate of 54/36, a conversion of 97.4% was reached.Example 2   When replacing TH with 1.28 g (10 mmol) of 2-acetyl TH under the same conditions as in Example 1. Did not react. Clearly, the 2-acetyl group is an inert group.Example 3   Under the same conditions as in Example 1, when TH was replaced with 0.82 g (10 mmol) of ME-FU, half After time, 1.32 g of 2-methyl-5 (tmb) FU had formed (68% conversion). The following analysis data I got: Example 4   In a 250 ml three-necked round bottom flask equipped with a magnetic stirrer, add 7.55 g (51 mm ol) of CTMP and then 5.0 g (51 mmol) of MeTH dissolved in 20 ml of DCM. 0.870 g (6.13 mmol) BF_Three・ OEt_TwoWas added slowly and the reaction was continued by GLC. GLC The data show that immediately after the addition of the Lewis acid, An alkylation product was formed.   The crude product was washed with water, dried and partially distilled (kugelrohr). 19 parses It was found that the MeOH of the reagent was converted to 2-methyl-5 (tmb) TH.Example 5   10 ml of 40:60 v / v hexane: DCM; 3.55 g (18.75 mmol) dissolved in 20 ml of the solvent TiCl_FourAnd 0.60 g (1.875 mmol) of DBTH dissolved in 20 ml of the solvent described above. The procedure of Example 1 was followed. The progress of the reaction was determined by GC. GC uses 5- (tmb) DBTH and And two single peaks of the same size (by GC-MS) for 5 '-(tmb) DBTH . A 75% conversion was achieved.Example 6   Experiment of PIB-functionalization for TH, BrTH, MeTH, DTHCE, DBTH, FU, and MeFU Was done.   -78 ° C CH_TwoCl_TwoA simple laboratory polymerization procedure in isobutene / hexane solvent mixture. The polymerization was carried out. After high monomer conversion (~ 100%), the aromatic ring system Was added. Changes in the structure of the chain ends are detected by the UV spectrum detector while performing GPC. And¹Investigated by 1 H NMR.   The experimental conditions for end capping with BrTH are as follows: Reactor 6.2 mmo l CTMP, 5.2 mmol 2,2'-bipyridyl, 150 ml CH_TwoCl_TwoAnd 350 ml of hexane I filled it. The solution was cooled to -78 ° C and 5 ml IB, then CH_TwoCl_Two(0.18M) 100ml TiCl_FourWas added. After 5 and 10 minutes, an additional 4 ml of IB was added. Polymerization Once complete, 100ml (pre-cooled) CH_TwoCl_Two31 mmol of BrTH dissolved in The reaction was monitored over time (precooled methanol was used as the coolant). make use of).   The experimental conditions for the end coupling with MeTH are as follows: mol CTMP, 2.4 mmol 2,2'-bipyridyl, 50 ml CH_TwoCl_TwoAnd 140 ml of hexane I filled it. The solution was cooled to -78 ° C and 5 ml IB, then CH_TwoCl_Two(0.24M) 50ml of TiCl dissolved in_FourWas added. After 5 and 10 minutes, another 5 ml of IB was added. Was. When the polymerization is complete, 50 ml (pre-cooled) CH_TwoCl_Two10 mmol dissolved in MeTH was added and the reaction was monitored over time (pre-cooled methanol As an agent).   Heterocyclic functions corresponding to the chain ends of polyisobutene (PIB) for both BrTH and MeTH Quantitatively converted to sex. The reaction between carbocation chain ends and these compounds is A relatively fast process; by UV analysis, 30-45 minutes for BrTH, respectively. MeTH was found to show quantitative conversion in 10-20 minutes.   ¹H-NMR spectrum is 6.55 (d, 2H), 6.80 (d, 2H) for 2-bromo-thiophene. Shows signals at 6.50 (d, 2H) and 6.55 (d, 2H) for 2-methyl-thiophene, Represents the formation of the corresponding chain ends for functionalization by BrTH and MeTH, respectively . An aromatic signal appears at the chain end of the heterocycle, which is opposite to the cationic chain end. -CH in PIBs quenched by unresponsive nucleophiles_Two-1.94 pp, characteristic of the group It is noteworthy that no signal appears at m. Spectral results (UV And NMR) show quantitative end quenching with BrTH and MeTH.   We also attempted to couple living PIB chains with bisthienyl. GPC UV signal indicates efficient addition of bisthienyl to the chain ends. However Depending on the molecular weight data, either DBTH or DTHCE show chain coupling. Not. The polymerization was warmed to room temperature in the presence of DBTH, but neither coupled. won.   Preliminary results also show that furan and 2-methylfuran also react with living PIB chains. I knew by experiment.Example 7   At -78 ° C, 33 mmol of CTMP, 49 mmol of DtBP and 131 mmol of TiCl as the ignition system_Four, Dissolved Using 600 ml of 60:40 v / v MCH / DCM and 1114 mmol of IB as the agent Was performed. After 1 hour, 31 mmol of MeTH was added. In 30 minutes, 2-methyl-5 (PIB) T A quantitative conversion to H was seen.Example 8   At -78 ° C, 16.5 mmol CTMP, 4.2 mmol DtBP and 63 mmol TiCl as ignition system_Four, Using 604 ml of 60:40 v / v MCH / DCM as solvent and 604 mmol of IB, isobutene Polymerization was performed. The polymer was produced with a number average molecular weight of 2244. After 1 hour, 7.3m mol of TH was added. At 30 minutes, a quantitative conversion was seen. The product is 2- (PIB) TH (M n was found to contain 2575) and 2-5-di (PIB) TH (Mn was 3121).Example 9   At -78 ° C, 16.8 mmol of CTMP, 24 mmol of DtBP and 65 mmol of TiCl as the ignition system_Four, Dissolved Isobutene weight using 600 ml of 60:40 v / v MCH / DCM and 566 mmol IB as agent Was performed. After 0.5 hour, 21 mmol of MeFU was added. In 30 minutes, 2-methyl-5 (PIB) A quantitative conversion to FU was seen.Example 10   At −78 ° C., 60 mmol of CTMP, 30.1 mmol of 2,2′-dipyridyl and 562.5 m mol of TiCl_FourUsing 1200 ml of 60:40 v / v MCH / DCM as solvent and 916 mmol of IB Then, isobutene polymerization was performed. After 1 hour, 50% w of the solution was removed. remaining Was added to 60 mmol of ethyl-2-thiophene acetate. 2 hours later, GPC ,¹H- and ゛¹³1 H-NMR confirmed the presence of the desired functional PIB.Example 11   Finished oil (zinc dithiophosphate as dispersant, detergent, overpressure antiwear agent) And 1% wt, 1500 Mn 2-methylthienyl capped with 3500 Mn PIB Antioxidant tests using isothermal differential calorimetry (DSC) analysis. went.   The analysis was performed using two Mettler-Toledo machines (DSC27HP). And 2.00 A ± 0.05 mg sample was placed in an aluminum pan and filled in a DSC device. And Brook Using a pressure and flow controller, set the oxygen pressure and flow rate to 3.4 MPa (500 psi), respectively. g) and 60 standard ml / min. By prioritizing ramp speed control, Was quickly heated to the test temperature of 200 ° C. Then, keep the sample at the test temperature. While monitoring the output. The induction time is calculated based on the derivative of the enthalpy graph. The tangent to the point where the rising slope of the heat generation peak is maximum Determined by sectioning.   As a result of the test, the average induction time of the production oil without 2-methylthienyl-capped PIB Is 10.9 minutes, whereas the average induction time of the sample is 13.7 minutes and 13.6 minutes, respectively. It turned out to be.   That is, these 2-methylthienyl-capped PIBs are effective antioxidants. You.Example 12   Example 10 (Mn = 3180; 3.0 mmol) and N, N-dimethyl-1,3-diaminopropane (DAP; 150 mmol) was placed in a three-necked flask equipped with a cooling tube, and heated at 130 ° C. for 10 hours. The reaction mixture was diluted with hexane (60ml) and washed with methanol (3x30ml). Organic Layer MgSO_FourDry over and filter. The solvent was removed to obtain a highly viscous substance.   Yield: 75%.   ¹³C-NMR: 170.1, 157.7, 133.4, 126.5 and 122.2 ppm, and 58.8, 58.4 and 45.3p At pm, the distinct signals of the bound thienyl and the bound DAP carbon, respectively .   IR: 1660cm^-1Manifestation of amide carbonyls and ester carbonyl There is no le. Elemental analysis: 1.07% w N, 0.90% w S.   For the product of Example 12, Bohlin VOR (viscosity-vibration-relaxation) rheometry in viscous mode. The dispersibility test was performed using the data. Put the sample (25g) in HVI-65 NS base oil Mixed on a hot plate and magnetic stir bar at 60-85 ° C . The active substance level was 2% w. 1.25g of carbon black (Cabot Vulcan X C72R) is weighed into a 150 ml Schott and hot mixed with a stir bar on top. The oil product was poured and discharged. Cover the bottle with a heating star set at 100 ° C. And then equilibrated by heating and stirring. And that hot trial Pour the mixture into a hot cup of the rheometer geometry and compare 0.2s for products containing carbon black^-1At a shear rate of 66% can reduce viscosity Do you get it. That is, these functional PIBs are effective dispersants.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10L 1/26 C10L 1/26 C10M 149/12 C10M 149/12 151/04 151/04 // C10N 30: 02 30:04 30:10 40:25 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW) , SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY , CA, H, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC , LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW

Claims (1)

[Claims] 1. a carbocation in which the living carbocationic polymerization system reacts with one or more aromatic ring systems   A method for functionalizing a polymer synthesized by on-polymerization. 2. The one or more aromatic ring systems are selected from 5-, 6- or 7-primary heterocycles.   The method of claim 1, wherein the method is characterized in that: 3. The one or more aromatic ring systems are selected from nitrogen, oxygen, phosphorus and sulfur.   The method according to claim 2, which is a heterocyclic ring system containing the above heteroatoms.   . 4. The one or more aromatic ring systems are selected from 6-π-electron ring systems.   3. A method according to claim 1 or claim 2. 5. The method according to any one of the preceding claims, wherein the one or more properties are different.   If the aromatic ring system is a heterocyclic pyrrole, furan, thiophene, oxazole,   Azoles, 1,3,4-thiadiazoles, pyrazoles, substitutions of these heterocycles,   And substituted and unsubstituted (benzo-) fused ring systems.   If there is a substituent, the substituent sterically links the remaining reactive moiety of the aromatic ring system.   A method which does not interfere and does not deactivate the aromatic ring system. 6. The method according to any one of the preceding claims, wherein the one or more properties are different.   When the aromatic ring system is a heterocyclic pyrrole, furan, thiophene,   Selected from the substituents, and if it has a substituent,   The group does not sterically hinder the remaining reactive moieties of the aromatic ring system and does not interfere with the aromatic ring system.   A method characterized by not being activated. 7. The above substituent is amino, hydroxy, alkoxy, aminocarbonyl, ant   Or alkyl group, or halogen atom.   7. The method according to item 5 or 6. 8. With a telechelic prepolymer capped by one or more functional end groups   Wherein the functional terminal group is a 5-atom, 6-π-electron heterocycle.   Telechelic prepolymer. 9. Branched or star-branched poly linked by one or more multifunctional coupling groups   Wherein the multifunctional coupling group is a 5-atom, 6-π-electron heterocycle.   A branched or star-branched polymer, characterized in that: 10. The component of claim 9 capped by one or more functional end groups.   A branched or star-branched polymer, wherein the terminal group is a 5-atom, 6-π-electron hetero.   A branched or star-branched polymer, which is a ring. 11. A major amount of lubricating base oil and a minor amount of any of claims 1 to 7   A lubricating oil composition containing a substituted or unsubstituted reaction product obtained by the method according to claim 1.   object. 12. A major amount of base fuel and a minor amount of any one of claims 1 to 7   A fuel composition comprising a substituted or unsubstituted reaction product according to the method described in (1). 13. An additive concentrate, comprising an inert carrier liquid and the total amount of said concentrate.   10 to 80% w by the method according to any one of claims 1 to 7.   Additive concentrate containing a substituted or unsubstituted reaction product. 14. Replacement or non-placement by the method according to any one of claims 1 to 7   Use of the reaction product as a dispersant, detergent or antioxidant additive or VI improver   for. 15. Claims in the synthesis of high molecular weight products including network and VI improvers   The telechelic prepolymer according to claim 8, or the component according to claim 10   Use of branched or star-branched polymers.