MXPA00001236A - Vinylidene-containing polymers and uses thereof - Google Patents

Abstract

Various vinylidene-containing polymers are obtained in the presence of a single-site catalyst. For example, the polymers include ethylene/isobutene copolymer, ethylene/propylene/isobutene terpolymer, ethylene/styrene/isobutene terpolymer, ethylene/ alpha -methyl-styrene/sobutene terpolymer, propylene/isobutene copolymer, styrene/isobutene copolymer, and alpha -methyl-styrene/isobutene copolymer. These polymers may be used to formulate lubricant oils.

Description

POLYMERS THAT CONTAIN VINYLIDENE AND ITS USES Field of the Invention The invention relates to polymers containing vinylidene, and to methods for making these polymers. The invention also relates to the applications of polymers containing vinylidene, especially in the formulation of lubricating oils. Background of the Invention Synthetic hydrocarbons have been used as lubricants for automotive, aviation and industrial applications. In the automotive industry, lubricating oils include motor oils, brake fluids, and lubricating greases. Motor oils for a car include two-stroke oils, four-stroke oils, and transmission oils. In the aviation industry, lubricating oils include turbine oils, piston engine oils, hydraulic fluids and lubricating greases. In industrial applications, lubricating oils are used as gas turbine oils, transmission oils, bearing and circulation oils, compressor oils, hydraulic oils, metalworking fluids, heat transfer and insulation oils, and lubricating greases. Polyisobutenes and poly-α-olefins are two notable synthetic hydrocarbons that have been used as lubricating oils. Poly-α-olefins have good flow properties at low temperatures, relatively high thermal and oxidative stability, low losses by evaporation at high temperatures, high viscosity index, good friction behavior, good hydrolytic stability, and good erosion resistance . The poly-α-olefins are non-toxic and are miscible with mineral oils and esters. Accordingly, poly-α-olefins are suitable for use in motor oils, compressor oils, hydraulic oils, transmission oils and greases. However, poly-α-olefins have limited biodegradability, and limited miscibility with additives. Accordingly, they may not be suitable for use as high performance transmission oils and fast biodegradation oils. Structurally, poly-α-olefins often include tertiary hydrogen, which is susceptible to oxidation. Accordingly, it would be desirable to eliminate the presence of tertiary hydrogen, to improve the oxidation resistance of synthetic hydrocarbons. Polyisobutenes are another type of synthetic hydrocarbon that has been used as lubricating oils. Polyisobutenes offer good lubrication properties and good resistance to corrosion. The poly-isobutenes are non-toxic and are miscible with mineral oils. However, polyisobutenes have a relatively low oxidation stability, and relatively poor flow properties at low temperatures. They also have relatively high evaporation losses, and low viscosity indexes. Accordingly, polyisobutenes are suitable for two-stroke engine oils, compressor oils, metal working lubricants, greases, and wire rope lubricants; but they are not suitable for most circulation system lubricants. In addition, it is known that polyisobutenes are depolymerized at elevated temperatures, a phenomenon known as "unzipping". In general, depolymerization occurs above 250 ° C. This unbundling phenomenon prevents the use of polyisobutenes at elevated temperatures. Accordingly, it would be desirable to avoid unbinding of the polyisobutenes, while retaining the benefits associated with the polyisobutenes. An α-olefin / isobutene copolymer may offer an alternative to polyisobutene and poly-α-olefins. For example, an ethylene / isobutene copolymer would not include tertiary hydrogen. Accordingly, this copolymer can have a better resistance to oxidation. In addition, the incorporation of ethylene units can prevent or alleviate the unbundling phenomenon associated with polyisobutenes. However, these copolymers have not been available, because many vinylidene olefins, such as isobutene, are not copolymerized in the presence of a Ziegler-Natta catalyst.

Accordingly, there is an unmet need to explore the possibility of making polymers containing vinylidene for different applications. SUMMARY OF THE INVENTION The embodiments of the invention described herein satisfy the above need, by providing different vinylidene-containing polymers, preferably obtained in the presence of a single-site catalyst. Methods for making and using the vinylidene-containing polymers are also provided herein. These polymers have a wide range of applications. The properties and advantages associated with the embodiments of the invention will become more apparent with the following description. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a 13C NMR spectrum of the copolymerization product of ethylene and isobutene obtained in accordance with the method described in Example 1. The chemical change at 51.2 ppm can be attributed to the presence of a diad of Isobutene in the resulting ethylene / isobutene copolymer. Figure 2 is a 13 C NMR spectrum of the copolymerization product of propylene and isobutene obtained by the method described in Example 3. Figure 3 is a 13 C NMR spectrum of the copolymerization product of styrene and isobutene obtained by the method described in Example 10.

Figure 4 is a 13C NMR spectrum of the copolymerization product of an α-methyl styrene and isobutene, obtained by the method described in Example 11. Description of the Embodiments of the Invention The embodiments of the invention provide different polymers of α-olefin / vinylidene and vinylidene / vini-lideno polymers. The polymers can be a copolymer, terpolymer, tetrapolymer, etc. The α-olefin / vinylidene polymers are hereby categorized into two groups: ethylene / vinylidene polymers, and higher α-olefin / vinylidene polymers, where "higher α-olefin" refers to the α-olefins with three or more carbon atoms per molecule. A feature of the ethylene / vinylidene polymer is that the polymer includes, within its chain, at least one diad of the vinylidene olefin. In some embodiments, the ethylene / vinylidene polymers may further include a repeating unit of ethylene within the polymer chain. A polymer generally includes many polymerization units of one or more monomers. A polymerization unit refers to a segment or portion of a polymer chain that repeats throughout the polymer chain. A diad refers to two adjacent monomers within a polymer chain. Accordingly, a vinylidene olefin diamide ("V") refers to a unit of [-V-V-] within a polymer chain. Examples of the ethylene / vinylidene polymer include, but are not limited to, ethylene / isobutene copolymers, ethylene / isobutene / propylene terpolymers, ethylene / isobutene / styrene terpolymers, and ethylene / isobutene / α-methylstyrene terpolymers. In contrast to the ethylene / vinylidene polymer, a vinylidene diad may or may not be present in the higher α-olefin / vinylidene polymer and in the vinylidene / vinylidene polymer according to the embodiments of the invention. Examples of the higher α-olefin / vinylidene polymer include, but are not limited to, propylene / iso-butene copolymers, styrene / isobutene copolymers, etc. An example of the vinylidene / vinylidene polymer is a copolymer of isobutene / α-methylstyrene. Suitable vinylidene olefins are represented by the following formula: R ^ -CH = CR 2 3 where R x is hydrogen or a hydrocarbyl group, and R 2 and R 3 are independently selected from an alkyl, aryl and aralkyl group. Preferably, R ± is a straight or branched chain saturated hydrocarbon radical with one to 12 carbon atoms. More preferably, Rx is hydrogen, R2 and R3 can be linear, branched or cyclic hydrocarbyl groups, with one to 100 carbon atoms. The hydrocarbyl groups may be substituted or unsubstituted. Optionally, R2 and R3 can be connected to form a cyclic structure. Accordingly, the term "vinylidene olefin" can include both monomers, such as isobutene, and macromers that make up the above representative structure. Although R1 R2 and R3 are essentially hydrocarbyl groups, the inclusion of a heteroatom, such as O, S, N, P, Si, halogen, etc., is allowed where these heteroatoms are sufficiently removed from the double bond so as not to interfere with the Polymerization reactions by coordination. Specifically, suitable vinylidene olefins include, but are not limited to, isobutene, 3-trimethyl-silyl-2-methyl-1-propene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-ethyl. -l-pentene, 2-methyl-1-hexene, 2-methyl-1-heptene, 6-dimethyl-amino-2-methyl-1-hexene, α-methyl styrene, 2, -dimethyl-pentene, and the like . In addition to the ethylene vinylidene olefin copolymers, the embodiments of the invention also provide terpolymers, tetrapolymers, etc., which contain vinylidene. These polymers are obtained by the copolymerization of an ethylene monomer, a vinylidene olefin monomer, and one or more additional olefinic monomers that are different from ethylene and the vinylidene olefin. With respect to suitable additional olefinic monomers, any olefin can be used. These include, but are not limited to, aliphatic olefins, cyclic olefins and aromatic olefins. Suitable cyclic olefins capable of having copolymerization include, but are not limited to, cyclopentene, norbornene, alkyl substituted norbornenes, cyclohexene, cycloheptene, etc. Examples of the additional suitable olefins also include one or more of the α-olefins of three carbon atoms and higher, and the styrene monomers substituted by hydrocarbyl, where the substituent is on the aromatic ring, internal olefins of four carbon atoms and higher, diolefins of four carbon atoms and higher, cyclic olefins and diolefins of five carbon atoms and higher, and substituted α-olefins of six carbon atoms and higher. Substituted α-olefins of six carbon atoms and suitable higher include those containing at least one atom of Groups IIIA to VIIA bonded with a carbon atom of the substituted α-olefin. Examples include allyltrimethylsilane, 4, 4, -trifluoro-1-butene, and the like. The use of the α-olefins containing functional group is within the scope of the invention, when these olefins can be incorporated in the same way as their α-olefin analogues do. In addition, masked α-olefin monomers, disclosed in U.S. Patent No. 5,153,282, may also be used, and the disclosure of this patent is incorporated herein by reference in its entirety. Preferred higher α-olefins include α-olefins having from three to 30 carbon atoms, preferably from 3 to 20 carbon atoms, but in a similar manner 1-olefin macromers having more than 30 carbon atoms. In general, suitable α-olefins are represented by the following formula: CH 2 = CHR 4 where R 4 can be any hydrocarbyl group, such as alkyl, aryl, or aralkyl. Some specific examples of the preferred α-olefins include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene , 4-methyl-1-pentene, 5-methyl-1-nonene, 3-methyl-1-pentene, 3, 5, 5-trimethyl-1-hexene and vinylcyclohexene. The preferred styrenic olefins are styrene and p-methylstyrene. In addition to the mono-olefins, the diolefins or polyenes can also be copolymerized with one or more vinylidene olefins. Examples of suitable diolefins or polyenes include straight-chain acyclic diolefins, branched acyclic diolefins, single-ring alicyclic diolefins, multi-ring alicyclic diolefins, of condensed and bridged ring, and alkenes substituted by cycloalkenyl. Preferred examples are 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, vinylcyclohexen-5-vinyl-2-norbornene, 4-ethylidene norbornene, and 1,4-norbornadiene. The vinylidene-containing polymers obtained in the embodiments of the invention generally have one or more of the following characteristics. First, the polymers have a relatively narrow molecular weight distribution ("MWD"), as indicated by the Mw / Mn. The molecular weight distribution is usually less than about 3.5, preferably less than about 2.5, and more preferably less than about 2. Second, the copolymers or terpolymers have a substantially random co-monomer distribution. In other words, the incorporation of co-monomers into the polymer substantially conforms to the Bernoullian statistical model. Accordingly, the polymers have a substantially uniform comonomer composition. Third, the polymers do not include the low molecular weight fractions in a significant amount. Other features and properties are apparent to experts in this field. The polymers according to the embodiments of the invention can be obtained in the presence of a single-site catalyst. It is known that some metallocene compounds are single-site catalysts. These metallocene compounds can include a Group IVB metal and Group VIIIB of the Periodic Table of the Elements. Optionally, a single site catalyst system may include a co-catalyst, such as an aluminoxane compound. For example, U.S. Patent Nos. 5,001,244, 5,272,236 and 5,278,272 disclose different single-site catalysts, and the disclosures of all of the above patents are incorporated by reference in their entirety hereof. U.S. Patent No. 5,866,665 discloses different single-site catalysts that can be used in the embodiments of the invention. The description of suitable catalysts from column 6, line 22 to column 11, line 50 of U.S. Patent No. 5,866,665, is incorporated by reference herein. Other suitable single-site catalysts are disclosed in U.S. Patent Application Serial No. 08 / 880,151, and the relevant part is incorporated by reference herein. In preferred embodiments, the single-site catalyst comprises a transition metal complex of Group IVB, a cation-generating co-catalyst, and an alkyl aluminum compound. Preferably, the transition metal complex of Group IVB is represented by the formula: (C5R nYsXpML2 where R is independently a linear or cyclic hydrocarbyl radical of one to 20 carbon atoms, m = 1, 2, 3, 4 or 5; n = 1, 2, or 3; Y or X is independently a heteroatom fraction containing a radical selected from the radicals -Si (R'R ") -, -N (R ') - / -P (R') - / -O-, -S- , or -C (R'R ") -, where R 'or R" is independently a hydrocarbyl radical of one to 20 carbon atoms, sop is independently 0 or 1, M is a metal atom of Group IVB; is halogen or a hydrocarbyl radical of one to 20 carbon atoms, and z = 4-np It is noted that both C5Rm (which is a substituted or unsubstituted cyclopentadienyl group) and X (which is not a cyclopentadienyl group), are directly linked with the transition metal M, while Y bypasses any two C5Rm groups, or a C5Rm group and a X group.

Preferably, the co-catalyst is a strong Lewis acid having the formula: B (C6F5) 3 or (C6H5) 3C + B ~ (C6F5) 4, and the alkyl aluminum compound is methylaluminoxane or trialkyl aluminum. The polymers obtained according to the embodiments of the invention can be cracked, hydrogenated or hydroisomerized. These processes are described in the pending United States patent application, Serial No. 08 / 880,151, and the pertinent part of the disclosure related to these processes is incorporated by reference herein. The polymeric products of cracking, hydrogenation, or hydroisomerization can be used as a component for lubricating oils. The following examples illustrate the embodiments of the invention, and do not limit the invention as described otherwise herein. It should be emphasized that any numerical values disclosed herein are approximate, and should not be construed as absolute. General Experimental Procedure All gaseous monomers were purified by passing them through a Matheson gas purifier, Model 6406-A. A 250 milliliter pressure reaction flask, with a magnetic stir bar, was completely purged with argon, and charged with 50 milliliters of dry toluene (distilled over potassium). The olefin monomers were pre-mixed in a 7 liter cylinder in a desired ratio, and heated to about 70 ° C overnight. The monomer mixture was fed to the reaction bottle at a certain temperature under a pressure of about 10 or about 20 psig. Then a solution of aluminum-tri-isobutyl (TIBA) in toluene was injected into the bottle with a syringe, followed by a metallocene catalyst in a toluene solution. Then triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph3CB (C6F5) 4) was added in a solution of toluene as co-catalyst. TIBA captures the humidity of the polymerization and of the alkylated metallocene precursors. A molar ratio of about 1: 1 of metallocene to co-catalyst was used. Polymerization of ethylene and isobutene was initiated after injection of the co-catalyst solution. Through the reaction, the temperature was maintained by a constant temperature bath with a circulator. H2 was used to control the molecular weight of the copolymer. The excess of monomers and hydrogen was continuously vented at a rate of about 10 to 20 milliliters / minute, to maintain a constant gas concentration in the reaction bottle. After one hour, the polymerization was quenched by injecting 10 milliliters of 2 percent acid methanol into the flask. The resulting solution was stirred for an extra hour. It was then washed three times with 200 milliliters of deionized water in a 500-milliliter separatory funnel. The organic layer was filtered through Celite to obtain a clear solution.

Subsequently, the toluene was removed on a rotary evaporator. The liquid copolymer product was further dried in a vacuum oven at about 75 ° C overnight, before being weighed and analyzed by nuclear magnetic resonance ("NMR") and gel permeation chromatography ("GPC"). Whenever isobutene was copolymerized with a liquid monomer, it was preferred that the monomers be premixed prior to injecting any catalyst solution. The heavy average molecular weight (Mw) and the numerical average molecular weight (Mn) were measured by gel permeation chromatography using a Waters 150CV gel permeation chromatography spectrometer equipped with a differential refractive index detector, and calibrated with standards of polystyrene. Three Shodex KF-806M columns and one Shodex KF-801 column were connected in series for an Mw between 3,000,000 and 1,000. The 13 C NMR spectra of the polymer samples were run on CDC13 at room temperature using a field strength of approximately 50 MHz, or in a trichlorobenzene / benzene-d6 mixture at about 80 ° C, using a field strength of about 500 MHz. The isobutene content, ie the percentage of IB, in an ethylene / isobutene copolymer, is calculated with the following formula: IB% = 100x2A / (2B + A) where A is the integration of the methyl resonance peak, and B is the integration of the methylene resonance peak. To help identify the nuclear magnetic resonance peaks, the software was used to simulate the 1C NMR chemical changes of the ethylene-isobutene copolymers. The software used was the software ACD / ChemSketch, version 3.50 / 09 of April of 1998, by Advanced Development Inc. According to the simulation by means of this software, a chemical change of approximately 51.2 ppm can be attributed to the presence of -E- IB-IB-E- in the polymer chain (E represents ethylene, and IB represents isobutene). Example 1 A 250 milliliter pressure reaction flask, with a magnetic stir bar, was completely purged with argon, and charged with approximately 50 milliliters of dry toluene (distilled over potassium). Ethylene, isobutene and hydrogen were previously mixed in a 7-liter cylinder, at a rate of about 8 percent, 82 percent, and 10 percent, respectively, and then heated to about 70 ° C overnight. The gas mixture was fed to the reaction flask at about 25 ° C under a pressure of about 10 psig. Then approximately 1.5 milliliters of 0.05 M tri-isobutyl aluminum (TIBA) were injected into a solution of toluene in the flask, with a syringe, followed by approximately 1 milliliter of Dow Insite® 3.75 x 10 ~ 3 M catalyst, [dimethylsilyl] dichloride. (tetramethyl-cyclopentadienyl) (tertiary butyl-a-ido)] titanium (ie, [(C5Me4) SiMe2N (t-Bu)] TiCl2) in a toluene solution, and finally approximately 1 milliliter of tetrakis (pentafluoro-phenyl) borate of triphenylcarbenium 3.75 x 10_3L M (Ph3CB (C6F5) 4) in a solution of toluene as co-catalyst. Polymerization of ethylene and isobutene was initiated after the injection of a co-catalyst solution. Throughout the reaction, the temperature was maintained by a constant-temperature bath with a circulator. Excess monomers and hydrogen were continuously ventilated at a rate of approximately 10 milliliters / minute to maintain a constant gas concentration in the flask. of reaction. After one hour, the reaction was quenched by injecting about 10 milliliters of 2 percent acid methanol into the flask, and the resulting solution was stirred for an additional hour. The product, together with toluene, was then washed with 3 x 200 milliliters of deionized water in a 500 milliliter separatory funnel. The organic layer was filtered through Celite to obtain a clear solution. Subsequently, the toluene was removed in a rotary evaporator to obtain an opaque viscous liquid. The activity of the polymerization was about 1.97 x 105 grams of polymer / (mol of Ti-hour). Analysis of 13 C NMR indicated that the product was a mixture of approximately 22.8 percent polyisobutene homopolymer, and approximately 77.2 percent ethylene isobutene copolymer. Figure 1 is the 13 C NMR spectrum of the copolymerization product of ethylene and isobutene. The ethylene / isobutene copolymer contained approximately 58.5 percent ethylene, and approximately 41.5 percent isobutene. The signal isolated at d 51.2 ppm in the 13C NMR of the polymerization product suggests the presence of the sequence --E-IB-IB-E - in the copolymer. Example 2 The procedure was essentially the same as in Example 1, except that a 1-liter Engineer Pressure Reactor autoclave was used, and different polymerization conditions. The reaction conditions are summarized in Table 1. A viscous liquid product was obtained. The 13 C NMR analysis indicated that the product was a mixture of approximately 23.0 percent polyisobutene homopolymer, and approximately 77.0 percent ethylene-isobutene copolymer. The copolymer contained about 75.2 percent ethylene, and about 24.8 percent isobutene. The polyisobutene has an Mw of about 780, and an MH / Mn of about 1.42. The ethylene-isobutene copolymer has an Mw of about 8.147, and an Mw / Mn of about 1.51. Once again, the isolated signal at d 51.2 ppm in the 13C NMR of the polymerization product suggests the presence of the sequence -E-IB-IB-E- in the copolymer.

Table 1 Example 3 The procedure was essentially the same as in Example 1. A mixture of propylene, isobutene and hydrogen gas was fed in a proportion of about 9 percent, 82 percent, and 9 percent, respectively, into the flask. of reaction containing about 50 milliliters of toluene at about 60 ° C, under a pressure of about 20 psig. Solutions of approximately 2 milliliters of 0.05 M TIBA, 4 milliliters of Insite® catalyst 15 x 10 ~ 3 M, and 4 milliliters of Ph3CB (C6F5) 4 15 x 10"3 M were used to initiate the polymerization. of the reaction system was continuously vented at a rate of about 20 milliliters / minute.After about one hour of reaction, a clear liquid with an activity of about 0.73 x 105 grams of polymer / (mol of Ti-hour) was obtained. The liquid has an Mw of about 3,316, and an Mw / Mn of about 3.00 The 13C NMR analysis of the liquid showed a propylene-isobutene copolymer formation Figure 2 is the 13C NMR spectrum of the propylene copolymerization product. and isobutene Example 4 The process was essentially the same as in Example 3, except that a gas mixture of monomers was fed at a rate of about 26 percent, 65 percent and 9 percent by weight. to propylene, isobutene and hydrogen, respectively, in the reaction bottle, and approximately 3 milliliters of 0.05 M TIBA were used to initiate the polymerization. After about one hour of reaction, a clear liquid with an activity of about 0.53 x 105 grams of polymer / (mol of Ti-hour) was obtained. The liquid has an Mw of about 4,900, and an Mw / Mn of about 5.77. 13C NMR analysis of the liquid showed formation of propylene-isobutene copolymer.

Example 5 The process was essentially the same as that of Example 1. A mixture of ethylene, propylene, isobutene and hydrogen gas was fed at a rate of about 9 percent, 4 percent, 78 percent and 9 percent, respectively , in the reaction flask containing approximately 50 milliliters of toluene at about 40 ° C under a pressure of about 20 psig. Approximately 2 milliliters of 0.05 M TIBA, 2 milliliters of Insite® catalyst 3.75 x 10 ~ 3 M and 2 milliliters of Ph3CB (C6F5) 4 solution 3.75 x 10 ~ 3 M were used to initiate the polymerization. The gas phase of the reaction system was continuously vented at a rate of approximately 20 milliliters / minute. After one hour of reaction, a clear liquid with an activity of about 4.89 x 105 grams of polymer / (mol of Ti-hour) was obtained. The 13 C NMR analysis of the liquid showed formation of the ethylene-propylene-isobutene terpolymer. Example 6 The procedure was essentially the same as in Example 5, except that the monomer-gas mixture was in a proportion of about 13.4 percent, 18 percent, 55.2 percent and 13.4 percent for ethylene, propylene, isobutene and hydrogen, respectively. After one hour of reaction, a clear liquid with an activity of about 3.47 x 105 grams of polymer / (mol of Ti-hour) was obtained.

The 13 C NMR analysis of the liquid showed formation of the ethylene-propylene-isobutene terpolymer. Example 7 The procedure was similar to that of Example 1. The reaction bottle was charged with approximately 50 milliliters of dry toluene and approximately 10 milliliters of styrene. Approximately 10 psig of a gas mixture was fed in a ratio of about 10 percent and 90 percent for ethylene and isobutene, respectively, into the flask, at about 50 ° C. Solutions of approximately 3 milliliters of 0.05 M TIBA, 4 milliliters of Insite® 0.015 M catalyst, and 4 milliliters of 0.03 M Ph3CB (C6F5) 4 were used to initiate the polymerization. The gas phase of the reaction system was continuously vented at a rate of approximately 10 milliliters / minute. After about an hour of reaction, a semi-solid with an activity of approximately 2.42 x 105 grams of polymer / (mol of Ti-hour) was obtained. The product has an Mw of about 3.127, and an MM / Mn of about 3.06. The differential scanning calorimetry ("DSC") study of the polymer indicated that an ethylene-styrene-isobutene terpolymer was formed. Example 8 The procedure was similar to Example 7. About 10 psig of a gas mixture was fed in a ratio of about 10 percent to 90 percent for ethylene and isobutene, respectively, in the flask, which contained approximately 1.04 x 10 ~ 4 moles of (C5Me5) TiCl3, and about 10 milliliters of α-methylstyrene at about 25 ° C. Solutions of about 3 milliliters of 0.05 M TIBA, and 5 milliliters of 0.03 M Ph3CB (C6F4) 4 were used to initiate the polymerization.The gas phase of the reaction system was continuously vented at a rate of about 10 milliliters / minute. After approximately one hour of reaction, a solid product with an activity of about 0.24 x 105 grams of polymer / (mol of Ti-hour) was obtained.The differential scanning calorimetry study of the polymer indicated that an ethylene terpolymer was formed. α-methylstyrene-isobutene Example 9 The process was essentially the same as in Example 8, except that 1.04 x 10 ~ 4 moles of Insite® catalyst was used in place of (C5Me5) TiCl3 as a catalyst for the polymerization. of one hour of reaction, the solid product was obtained with an activity of 0.41 x 105 grams of polymer / (mol of Ti-hour) .The differential scanning calorimetry study of the materi al indicated that an ethylene-α-methylstyrene-isobutene terpolymer was formed. Example 10 The procedure was similar to that of Example 1. A 250 milliliter pressure reaction flask, with a magnetic stir bar, was completely purged with argon, and charged with approximately 50 milliliters of dry toluene and 10 milliliters of styrene. Then about 10 psig of isobutene was fed into the bottle at about 50 ° C. Approximately 3 milliliters of 0.05 M TIBA, 4 milliliters of 0.0152 M (C5Me5) TiCl3 in a toluene solution, and 4 milliliters of 0.0152 M Ph3CB (C6F5) 4 were used to initiate the polymerization. After about one hour of reaction, a clear liquid with an activity of about 1.21 x 105 grams of polymer / (mol of Ti-hour) was obtained. Analysis of 13 C NMR of the liquid showed that a substantially random styrene-isobutene copolymer was formed, and that it contained approximately 67 percent isobutene, and approximately 33 percent styrene. Figure 3 is a 13 C NMR spectrum of styrene and isobutene copolymerization product. The liquid product had an Mw of about 2,755 and an MH / Mn of about 3.62. Example 11 The procedure was similar to that of Example 10. A 250 milliliter pressure reaction flask, with a magnetic stir bar, was completely purged with argon, and charged with approximately 1.04 x 10 ~ 4 moles of (C5Me5 ( TiCl3), and approximately 10 milliliters of α-methylstyrene Approximately 10 psig of isobutene was fed into the bottle at approximately 25 ° C. Solutions of approximately 3 milliliters of 0.05 M TIBA, and 5 milliliters of Ph3CB (C6F5) 4 0.02 were used. M to initiate the polymerization After approximately one hour of reaction, a clear liquid with an activity of about 0.51 x 105 grams of polymer / (mol of Ti-hour) was obtained.The analysis of 13C NMR of the liquid indicated that it was formed a copolymer of substantially randomized α-methylstyrene-isobutene, and containing about 59 percent isobutene, and about 41 percent α-methylstyrene, Figure 4 is a 13C spectrum NMR of the α-methylstyrene / isobutene copolymer. The liquid had an Mw of about 1,211, and an Mw / Mn of about 3.85. Example 12 This example compares the oxidation stability of a commercially available poly-a-olefin base feed., with a base oil formulated with a hydrogenated ethylene-isobutene copolymer obtained in Example 2. The commercially available poly-α-olefins were obtained under the trade name Mobil 1001, and are referred to as PAO 100. Two samples were made from the commercially available poly-α-olefin: the first sample included PAO 100 as the main component, and approximately 0.25 weight percent of an anti-oxidant; and the second sample included PAO 100, and approximately 0.50 weight percent of an anti-oxidant. The anti-oxidant used was 2,6-di-butyl t-4-methylphenol. Two additional samples were made from the hydrogenated ethylene / isobutene copolymers of Example 2. The hydrogenation of the ethylene / isobutene copolymers was performed by the method described in Example 4 of the United States patent application Serial No. 08 / 880,151 (of which this application claims priority). The hydrogenated ethylene / isobutene copolymers were mixed with about 0.25 weight percent and about 0.50 weight percent 2,6-dibutyl t-4-methylphenol as an anti-oxidant, respectively, to make the third and fourth samples. The oxidation resistance of these four samples was studied by pressurized differential scanning calorimetry. In this method, a sample was loaded into a sample chamber filled with oxygen at approximately 500 psi. The sample was heated to a temperature of about 175 ° C. The differential scanning calorimetry apparatus detected and recorded the induction time that was needed for the sample to be oxidized under these conditions. The induction time is a general indicator of the oxidation stability of the sample. The longer the induction time, the more resistant to oxidation the sample is in general. Table 2 shows the average induction time for the four samples measured.

Table 2 It is surprising that the ethylene / isobutene copolymers have substantially better oxidation resistance than PAO 100 for the same amount of anti-oxidant. As such, the ethylene / isobutene copolymers obtained in accordance with the embodiments of the invention can be used as a component of lubricating oils. The vinylidene-containing polymers obtained according to the embodiments of the invention can be used in lubricating oils in amounts of about 0.1 weight percent to about 99 weight percent. Lubricating oils may also contain various conventional additives in the amounts required to provide different functions. These additives include, but are not limited to, ashless dispersants, metal or overbased metal detergent additives, zinc dihydrocarbyl dithiophosphate, anti-wear additives, anti-oxidants, melting point depressants, corrosion inhibitors, fuel economy or friction reduction, and the like. Suitable ashless dispersants may include, but are not limited to, borated polyalkenyl or polyalkenylsuccinimide, where the alkenyl group is derived from an olefin of three to four carbon atoms, especially polyisobutenyl having a number average molecular weight of approximately 7,090 to 5,000. Other well known dispersants include the oil soluble polyester polyols of hydrocarbon substituted succinic anhydride, for example, polyisobutenylsuccinic anhydride, and the oil soluble oxazoline and oxazoline lactone dispersants derived from hydrocarbon substituted succinic anhydride and amino alcohols di- replaced. Lubricating oils typically contain from about 0.5 to about 5 weight percent of ashless dispersant. Suitable metal detergent additives are known in the art, and may include one or more of calcium-soluble, magnesium-and-barium-soluble phenates, overbased oils, sulfurized phenates, and sulfonates (especially alkyl substituted benzene sulfonates of 16 to 50 atoms. carbon, or toluenesulfonic acids having a total base number of about 80 to 300). These overbased materials can be used as the sole metal detergent additive, or in combination with the same additives in the neutral form; but the global metal detergent additive must have a basicity represented by the above total base number. Preferably, they are present in amounts of about 3 to 6 weight percent with a mixture of sulfurized phenate of overbased magnesium and neutral calcium sulphided phenate (obtained from the alkyl phenols of nine or 12 carbon atoms). Suitable anti-wear additives are zinc dihydro-alkyldithiophosphates soluble in oil with a total of at least five carbon atoms, and are normally used in amounts of about 1 to 6 weight percent. Other suitable conventional viscosity index improvers, or viscosity modifiers, are olefin polymers, such as polybutene, polymers and copolymers and hydrogenated terpolymers of styrene with isoprene and / or butadiene, polymers of alkyl acrylates or alkyl methacrylates, copolymers of alkyl methacrylates with N-vinylpyrrolidone or dimethylaminoalkyl methacrylate, polymers subsequently grafted with ethylene propylene with an active monomer, such as maleic anhydride, which can be further reacted with alcohol or with an alkylene polyamine, styrene-maleic anhydride polymers subsequently reacted with alcohols and amines and the like. These are used as required to provide the desired viscosity range in the finished oil, according to the known formulation techniques. Examples of suitable oxidation inhibitors are hindered phenols, such as 2,6-dibutyl t-paracresol, sulfurized phenols of amines and alkylphenothiazones. Normally, a lubricating oil may contain from about 0.01 to 3 weight percent of oxidation inhibitor, depending on its effectiveness. Corrosion inhibitors are employed in very small proportions, such as from about 0.1 to 1 weight percent, with suitable corrosion inhibitors exemplified by the aliphatic succinic acids or anhydrides of nine to 30 carbon atoms, such as dodecenylsuccinic anhydride. Anti-foaming agents are typically polysiloxane-silicone silicone polymers present in amounts of about 0.01 to 1 weight percent. Melt point depressants are generally used in amounts of from about 0.01 to about 10.0 weight percent, more typically from about 0.1 to about 1 weight percent, for most base supplies of mineral oil of a lubricating viscosity . Illustrative melting point depressants which are commonly used in lubricating oil compositions are polymers and copolymers of normal alkyl methacrylate and normal alkyl acrylates, copolymers of normal dialkyl fumarate and vinyl acetate, alpha-olefin copolymers, alkylated naphthalenes , copolymers or terpolymers of alpha-olefins and styrene and / or alkylstyrene, styrene-dialkyl-male copolymers, and the like. The polymers obtained in accordance with the embodiments of the invention are useful in numerous applications, depending on the type of polymers and their compositions. The polymers can be in the form of liquid, semi-solid or solid. The polymers can be elastomeric, plastic or plastomeric. The molecular weight of the polymers can be from about 200 to more than 2,000,000. The polymer can be cracked, hydrogenated or hydroisomerized. Polymeric products from cracking, hydrogenation or hydroisomerization can be used as a component for lubricating oils and other useful products. In accordance with the embodiments of this invention, vinylidene copolymers and terpolymers containing aliphatic α-olefins are useful as pressure sensitive adhesives and hot melt adhesives. The styrene-containing product of this invention possesses the properties required for a printable or flattable coating. Polymers containing vinylidene with unconjugated diolefin co-monomer are useful as sealants, elastomers and viscosity improvers. It is noted that a vinylidene / ethylene copolymer is substantially free of tertiary hydrogen and, therefore, must be resistant to oxidation and degradation catalysed by a transition metal. Due to the absence of reactive tertiary hydrogen, the lubricating oils formulated from these polymers should have a better oxidation stability at high temperature. As demonstrated above, the embodiments of the invention provide different vinylidene-containing polymers. Among them are the vinylidene / α-olefin polymers and the vinylidene / vinylidene polymers. These polymers may optionally include an additional olefin monomer that is different from the vinylidene olefin and the α-olefin. In the case of an ethylene / vinylidene polymer, it includes at least one vinylidene diad. For other types of polymers, there may or may not be a vinylidene olefin diad. When used as a component of a lubricating oil, polymers can offer one or more of the following advantages: better oxidation resistance, better thermal stability, desired viscosity, lower melting point, lower cold start viscosity, Higher ignition point, and effectiveness for cost. It is important to note that the application of polymers containing vinylidene is not limited only to the formulation of lubricating oils. Vinylidene-containing polymers can also have a variety of applications in the manufacture of air care products, skin care products, hair care products, cosmetics, household products, cleaners, polishers, fabric care products, textile coatings, textile lubricants, automotive products, car cleaners and polishers, additives of fuel, oil additives, candles, pharmaceuticals, suspending agents, sun care products, insecticides, gels, hydraulic fluids, transmission fluids, modifiers for polymers, biodegradable products, motor oils, etc. Additional applications may include uses such as hot melt adhesive, printable coating, sealant, elastomer, and viscosity improver. Although the invention has been described with respect to a limited number of embodiments, modifications and variations thereof exist. For example, a polymer that includes two or more vinylidene olefins without the presence of an α-olefin, can similarly be produced using the methods described herein. Copolymers, terpolymers and tetrapolymers can also be synthesized which include only vinylidene olefins in a similar manner. Although the polymers according to the embodiments of the invention are made in the presence of a single-site catalyst system, other catalyst systems can also be used, as long as they produce the polymers with characteristics similar to those described herein. The appended claims are intended to cover all variations and modifications that fall within the scope of the invention.

Claims (35)

1. CLAIMS 1. A polymer, comprising polymerization units of an ethylene monomer and a vinylidene olefin monomer, where the polymer has a polymer chain that includes a recurring unit of [-EV-] and at least one unit of [-VV] -]; where E represents the ethylene monomer, and V represents the vinylidene olefin monomer.
2. 2. The polymer of claim 1, wherein the polymer chain further includes a recurring unit of [-E-].
3. 3. The polymer of claim 1, wherein the vinylidene monomer is selected from the group consisting of vinylidene aliphatic olefins, cyclic vinylidene olefins, and vinylidene aromatic olefins.
4. 4. The polymer of claim 1, wherein the vinylidene olefin has the formula R1-CH = CR2R3, wherein Rx is H, alkyl, aryl or aralkyl, and R2 and R3 are independently selected from alkyl, aryl and aralkyl.
5. The polymer of claim 1, wherein the vinylidene olefin is selected from the group consisting of 2-methyl-1-propene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-methyl. hexene, and a-methyl-styrene.
6. The polymer of claim 1, wherein the polymer is a copolymer of ethylene and isobutene or a copolymer of ethylene and α-methyl-styrene.
7. The polymer of claim 1, wherein the polymer is a terpolymer that further includes a third olefin monomer, and the third olefin monomer is different from the ethylene monomer and the vinylidene olefin monomer.
8. The polymer of claim 7, wherein the third olefin monomer is selected from the group consisting of aliphatic olefin, aromatic olefin and cyclic olefin.
9. 9. The polymer of claim 7, wherein the third olefin monomer is selected from the group consisting of propylene, l-butene, 1-pentene, l-hexene, 1-heptene, 1-octene, 1-nonene, 1- decene, and styrene.
10. The polymer of claim 7, wherein the polymer is a terpolymer of ethylene, propylene, and isobutene, a terpolymer of ethylene, styrene, and isobutene, or a terpolymer of ethylene, α-methyl styrene, and isobutene.
11. 11. A polymer comprising polymerization units of a vinylidene olefin monomer and a monomer of a higher α-olefin, wherein the vinylidene olefin has the formula R1-CH = CR2R3, wherein R? is H, alkyl, aryl or aralkyl, and R 2 and R 3 are independently selected from alkyl, aryl and aralkyl, where the higher α-olefin has three or more carbon atoms and is represented by the formula CH 2 = CHR 4, in which R 4 it is alkyl, aryl or aralkyl.
12. 12. The polymer of claim 11, wherein the polymerization units include a third olefin monomer different from the α-olefin and the vinylidene, with the proviso that the second olefin has three or more carbon atoms.
13. The polymer of claim 11, wherein the α-olefin monomer is selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1 -decene, and styrene.
14. The polymer of claim 12, wherein the third olefin monomer is selected from the group consisting of propylene, l-butene, 1-pentene, l-hexene, 1-heptene, 1-octene, 1-nonene, 1- decene, styrene, 2-methyl-1-propene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, or α-methyl styrene.
15. 15. A copolymer of α-methyl styrene and isobutene.
16. 16. A cracked polymer obtained by cracking the polymer of claim 1, 7, 11, 12, or 15.
17. 17. A hydrogenated polymer obtained by hydrogenating the polymer of claim 1, 7, 11, 12, or 15.
18. 18. A polymer hydrogenated obtained by hydrogenating the cracked polymer of claim 16.
19. 19. A hydroisomerized polymer obtained by hydroisomerizing the polymer of claim 1, 7, 11, 12 or 15.
20. 20. A manufacturing article, comprising the polymer of claim 1 , 11, 12 or 15.
21. 21. The article of manufacture of claim 20, wherein the article of manufacture is lubricant., hot melt adhesive, printable coating, sealer, elastomer, plastic, or viscosity improver.
22. 22. A method for making a vinylidene-containing polymer, comprising: polymerizing a vinylidene olefin monomer and an α-olefin monomer having three or more carbon atoms in the presence of a single-site catalyst, wherein the vinylidene olefin has the formula R1-CH = CR2R3, in which Rx is H, alkyl, aryl or aralkyl, and R2 and R3 are independently selected from alkyl, aryl and aralkyl, where the α-olefin has the formula CH2 = CHR4, in the which R4 is alkyl, aryl or aralkyl.
23. 23. A method of making an isobutene-containing polymer, comprising: polymerizing an isobutene monomer and a vinylidene olefin monomer in the presence of a single-site catalyst.
24. The method of claim 22 or 23, wherein the single site catalyst includes a metallocene compound having a transition metal of group IVB of the Periodic Table.
25. 25. The method of claim 24, wherein the single site catalyst further includes an aluminoxane compound.
26. 26. The method of claim 22 or 23, wherein the single-site catalyst comprises transition metal complexes of group IVB, a co-catalyst that generates a cation, and an aluminum alkyl compound.
27. The method of claim 24, wherein the metallocene compound is represented by the formula (C5Rm) nYsXpMLz wherein R is independently a linear or cyclic hydrocarbyl radical of 1 to 20 carbon atoms; m = 1, 2, 3, 4 or 5; n = 1, 2, or 3; Y or X are independently a heteroatom fraction containing a radical selected from -Si (R'R ") -, N (R ') -, -P (R') -, -O-, -S-, or -C (R'R ") -, where R 'or R" are independently a hydrocarbyl radical of one to 20 carbon atoms, so P are independently 0 or 1, M is a metal atom of group IVB, and L is halogen or a hydrocarbyl radical of 1 to 20 carbon atoms, yz = 4 np, where both CjR ,,, and X are directly linked to the transition metal M, and Y bypasses either two CsRm groups or one C5Rm group and one group X.
28. 28. The method of claim 26, wherein the cocatalyst is a strong Lewis acid having the formula: B (C6F5) 3 or (C6H5) 3C + B- (C6F5) 4.
29. 29. The method of claim 26 wherein the alkyl aluminum compound is methylaluminoxane or trialkyl aluminum 30.
30. The method of claim 22 or 23, further comprising cracking the vinylidene-containing polymer to produce a vinylidene-containing polymer.
31. The method of claim 22 or 23, further comprising hydrogenating the vinylidene-containing polymer to produce a hydrogenated vinylidene-containing polymer.
32. 32. The method of claim 30, further comprising hydrogenating the cracked vinylidene-containing polymer.
33. The method of claim 22 or 23, further comprising hydroisomerizing the vinylidene-containing polymer to produce a hydroisomerized vinylidene polymer.
34. 34. The method of claim 22 or 23, wherein a third olefin monomer is copolymerized with the vinylidene olefin and the α-olefin to form a terpolymer.
35. 35. A method of making a lubricating oil, comprising: mixing the polymer of claim 1, 11, 12 or 15 with an additive.