OLEFIN OLIGOMERIZATION PROCESS AND CATALYST

Abstract: Alpha-olefin oligomer is prepared by contacting an alpha-olefin monomer which contains from about 8 to about 20 carbon atoms with a heterogeneous catalyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, (ii) a boron trihalide, preferably BF3, and, optionally (iii) an organomagnesium halide.

Description: OLEFIN OLIGOMERIZATION PROCESS AND CATALYST TECHNICAL FIELD This invention relates generally to the preparation of alpha-olefin oligomers which are useful as synthetic lubricants and functional fluids and more particularly to a novel catalyst system and a novel catalytic process for conducting such oligomeπzations BACKGROUND Alpha-olefin oligomers and their use as synthetic lubricants are well- known The oligomers are usually hydrogenated in order to improve their stability Hydrogenated oligomers produced from 1-alkenes, especially linear 1-alkenes having in the range of about 8 to about 14 carbon atoms are generally deemed most suitable for use as synthetic lubricants and fluids Hydrogenated oligomer oils with viscosities of about 2-10 cSt at 100°C are typically used for general lubricating oil applications These materials are, in general mixtures of different percentages of dimer, trimer tetramer pentamer and, in the case of the higher viscosity products in this range, higher oligomers as well For some lubricant applications, hydrogenated oligomers with still higher viscosities are desired While various types of alpha-olefin oligomeπzation catalysts have been disclosed, catalysts based on boron trifluoride have proven most useful Patent literature on BF 3 -based alpha-olefin oligomeπzation includes U S Pat Nos 2,806,072, 3 149.178, 3 382,291 , 3,769,363, 3,997,621 4,172,855, 4,218,330, 4,436,947, 4,982,026, 5,068,487, 5,191 ,140, 5,396,013, and 5,420,373 As indicated in these disclosures, a suitable promoter is used with the BF 3 to render it suitably effective for effecting the oligomenzation Although the boron tnfluoride-based catalyst systems exemplified by the above patents are effective, they are not without drawbacks or deficiencies Chief among these are the problems of recovery and disposal of the catalyst residues See for example U S Pat Nos 4,213,001 4,263,467, 4,308,414, 4,384,162, 4,394,296, 4,433,197, 4,454,366 and 4,981 ,578 which describe various ways of coping with these problems U S Pat No 5,288,677 discloses immobilized Lewis acid catalysts and their use as catalysts for the polymerization of isobutylene, mixed butenes and copolymenzation of monomers including 1 -butene, ethylene and 1 - hexene One of the catalysts used for polymerization of isobutylene is hydroxylated polybutene-1 copolymer which has been reacted with BF 3 in a manner to form a sigma (σ) bond between the boron and oxygen atoms For ease of description this copolymer is depicted in simplified form in the patent as PB-O-BF 2 ("PB" referring to polybutene) Additional experiments have been conducted using PP-0-BF 2 catalyst systems, such as PP-0-BF 2 /n-BuOH, PP-O-BF 2 /n-BuOH/CH 2 CI 2l PP-0-BF 2 /HCI; PP-0-BF 2 /HCI/CH 2 CI 2 , PP-0-BF 2 /HCI, PP-0-BF 2 /t-BuCI, and PP-0-BF 2 /BF 3 (gaseous BF 3 ) where "PP" refers to polypropylene, n-BuOH is n-butanol, CH 2 CI 2 is methylene chloride, and t-BuCI is tertiary butyl chloride, and where the BF 3 was in gaseous form This work has shown that all of these additional systems show good reactivity in polymerizing isobutylene and styrene Unfortunately, all of these systems showed no reactivity to 1-octene SUMMARY OF THE INVENTION This invention in one of its embodiments provides a new catalytic process for producing 1 -olefin oligomers which utilizes a stable catalyst system that is very reactive at relatively high temperatures, and that is readily recoverable and reusable in further oligomenzation reactions In accordance with this embodiment, a 1 -olefin having in the range of about 8 to about 20, and preferably about 8 to about 14 carbon atoms, or a mixture of two or more such 1 -olefins, is oligomerized by contact with a catalyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, and (ii) a boron tnhalide, most preferably boron trifluoride, and, optionally, (iii) an organomagnesium halide Studies have indicated that the components (i) and (ii) form a complex under ordinary ambient temperature conditions The oligomeπzation process of this invention is very easy to carry out Oligomenzation proceeds readily in short reaction periods and at convenient reaction temperatures, including room temperature This invention in another of its embodiments provides a new heterogeneous catalyst system formed form (i) a solid olefin polymer having a linear backbone and a plurahty of pendant omega-hydroxyalkyl groups, (n) an organomagnesium halide, and (iii) a boron triha de, most preferably boron trifluoride The available chemical evidence supports the view that the unification of these components results in the formation under ordinary ambient room temperature conditions of a novel complex which, using polypropylene having a plurality of pendant substituents as a typical example, may be depicted as follows (-CH-CHj-), (-CH-CH 2 -) y where X is halide, x is an integer representing the number of the substituted polypropylene units in the molecule, y is an integer representing the number of unsubstituted polypropylene units in the molecule, and n is an integer representing the length of the carbon chain of the pendant substituents This catalyst system or complex is readily prepared by combining a Grignard reagent with a solid olefin polymer having pendant omega- hydroxyalkyl groups and then combining a boron tnhalide, preferably boron trifluoride, with the resultant product Both steps are preferably conducted in a suitable anhydrous medium, such as a hydrocarbon diluent, under an inert atmosphere, using the substituted olefin polymer in finely-divided or particulate form Both steps can be conducted at room temperature The process for producing the catalyst system or complex forms still another embodiment of this invention One important advantage of the invented process and catalyst system is that the solid catalyst system or components can be recovered and reused repeatedly in batch-type operations and can be used for long periods of time in continuous or semi-continuous operations Thus, in a batch-type process, the solid catalyst material can be readily separated from the product by filtration or like physical separation procedure, and used in ensuing operations In continuous and semi-continuous operations the solid catalyst material can be used as a bed through which the olefin is passed When using a catalyst formed from solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups and a boron tnhalide without organomagnesium halide, boron tnhalide is periodically introduced to the oligomenzation at intervals sufficient to maintain the catalytic activity of the catalyst system When using catalyst formed from the olefin polymer, boron tnhalide and organomagnesium halide, the solid catalyst complex is kept in an anhydrous, inert environment when not in use In oligomeπzations utilizing the catalyst complex, a fresh charge of boron tnhalide is completely unnecessary, at least during the extended periods of time during which the catalyst retains suitable catalytic activity However, a fresh charge of boron tnhalide can be introduced into the mixture at any suitable time, if desired Another feature of this invention is the fact that by utilizing appropriate combinations of reaction time and temperature, oligomer product mixtures having different proportions of dimers, trimers, tetramers, etc , can be formed For example, by increasing the temperature products having higher proportions of dimer and trimer and smaller proportions of tetramer and higher oligomers can be formed Similarly, by keeping the temperature relatively low and increasing the reaction period the proportion of dimer in the product mixture can be decreased. The above and other embodiments and features of this invention will become still further apparent from the ensuing description and appended claims FURTHER DESCRIPTION Olefins for Oligomenzation The olefins used in making the oligomers are predominately (at least 50 mole %) C 8 -C 20 and preferably predominately C 8 -C 14 straight chain (i e linear) monoolefmically unsaturated hydrocarbons in which the olefinic unsaturation exists in the 1- or alpha-position of the straight chain Such alpha-olefins are available as articles of commerce, and can be made by thermal cracking of paraffinic hydrocarbons or by well-known Ziegler ethylene chain growth technology Individual olefins can be used as well as mixtures of such olefins Examples of olefins that can be used are 1-octene, 1- nonene, 1-decene, 1-undecene, 1-dodecene, 1-trιdecene, 1-tetradecene, 1- pentadecene, 1-hexadecene, 1-octadecene, 1-eιcosene and mixtures of two or more of such 1 -olefins Remotely branched 1 -olefins such as 5-methyl-1- heptene, 6-methyl-1-heptene, 6-methyl-1-octene, 7-methyl-1-octene, 6,7- dιmethyl-1-octene, 7,7-dιmethyl-1-octene, 8-methyl-1 -nonene, and like 1- olefins can also be used especially when used together with linear 1 -olefins The more preferred olefins are linear alpha-olefin monomers containing about 8-14 carbon atoms The most preferred 1 -olefin monomers are 1-octene, 1- decene, 1-dodecene and mixtures of any two or all three of these Minor amounts of up to about 50, and usually less than 25, mole % of internal and/or vinylidene olefins can be present in the olefin monomers The oligomeπzable olefins used in the practice of this invention can also be mixtures or combinations of olefins having an average in the range of about 8 to about 20 carbon atoms per molecule, such as mixtures of octenes, decenes and dodecenes having an average carbon content per molecule falling in this range Olefin Polymer with Pendant Omega-Hydroxyalkyl Groups The olefin polymer having pendant omega-hydroxyalkyl groups can be prepared in a two-stage operation In the first stage a polymer having hydrocarbyl-borohydrocarbyl groups depending from the backbone is formed This involves either homopolymeπzmg or copolymenzing a hydrocarbyl borane monomer having an omega-alkenyl group (e g , B-(5-hexen-1-yl)-9- BBN, B-(7-octen-1-yl)-9-BBN, etc ) as described for example in U S Pat Nos 4,734,472 and 4,751 ,276 The polymerization is effected using a suitable Ziegler-Natta catalyst system such as TιCI 3 AA/AIEt 2 CI (where "AA" means aluminum activated) Procedures for producing the hydrocarbylborane monomers are also described in these two patents When forming the copolymers, the hydrocarbyl borane having an omega-alkenyl group is copolymeπzed with at least one straight chain 1 -olefin, preferably a straight chain 1 -olefin having 3-10 (more preferably 3-6) carbon atoms or a mixture of any two or more of these, most preferably propylene The copolymers formed in this first stage may contain from 0 1 to 99 9 mole % of units derived from the hydrocarbyl borane monomer and from 99 9 to 0 1 mole % of units derived from the straight chain 1-olefιn(s) Preferred copolymers have from about 1 to about 15 mole % of units derived from the hydrocarbyl borane monomer and from about 99 to about 85 mole % of units derived from the straight chain 1-olefιn(s) In the second stage the hydrocarbylborane-substituted polymer formed in the first stage is reacted with an inorganic base and a peroxide, preferably sodium hydroxide and hydrogen peroxide, to form the olefin polymer having pendant omega-hydroxyalkyl groups Once again U S Pat Nos 4,734 472 and 4,751 ,276 provide a detailed description of this synthesis procedure Suitable olefin polymers having pendant omega-hydroxyalkyl groups comprise poly(1-alken-τ_-ol) polymers in which the 1-alken-τπ-ol units contain 6 to about 12 carbon atoms each, and poly(1-alkene-co-1-alken-__-ol) polymers in which the alkene units contain 3 to about 10 carbon atoms each and the l-alken-ra-ol units contain 6 to about 12 carbon atoms each The homopolymers are typified by poly(1-hexen-6-ol) and poly(1-octen-8-ol) The copolymers include poly(1-butene-co-1-alken-τσ-ol) polymers, such as poly(1- butene-co-1-hexen-6-ol) and poly(1-butene-co-1-octen-8-ol), poly(1-pentene- co- 1-alken-τπ-ol) polymers, such as poly(1-pentene-co-1-hexen-6-ol) and poly(1-pentene-co-1-hepten-7-ol), and poly(1-hexene-co-1-alken-τσ-ol) polymers, such as poly(1-hexene-co-1-hexen-6-ol) and poly(1-hexene-co-1- decen-10-ol) Particularly preferred olefin polymers having pendant omega- hydroxyalkyl groups are poly(propylene-co-l-alken- π-ol) polymers, such as poly(propylene-co-1-hexen-6-ol), poly(propylene-co-1-hepten-7-ol), poly(propylene-co-1-octen-8-ol), poly(propylene-co-1-nonen-9-ol), and poly(propylene-co-1-decen-10-ol) These propylene-deπved copolymers when suitably prepared have crystallinity and brush-like molecular structures with the hydroxyl groups at the ends of flexible side chains Note in this connection, T C Chung, Polymer News. 1993, Volume 18, pages 38-43 and Chemtech, 1991 , Volume 21 , pages 496-499 Thus they are capable of forming highly active catalytic complexes according to this invention Poly(propylene-co-1-hexen-6-ol) is a particularly preferred hydroxyalkyl olefin polymer for use in the practice of this invention Catalyst Systems or Complexes with Qrαanomaαnesium Halide In the embodiment of this invention in which organomagnesium halide is employed in forming the catalyst system or complex, the olefin polymer having pendant omega-hydroxyalkyl groups is first reacted with an organomagnesium compound, preferably an organomagnesium halide, commonly known as a Grignard reagent The olefin polymer is preferably treated in a particulate or finely-divided state while suspended in an anhydrous inert medium such as paraffinic, cycloparaffinic or aromatic hydrocarbon, and under an inert atmosphere The treatment is normally conducted at ordinary room temperatures Reaction periods of up to 8 hours or more at room temperature can be used Suitable hydrocarbylmagnesium halides include alkylmagnesium chlorides and bromides, such as ethylmagnesium chloride, propylmagnesiurp chloride, butylmagnesium chloride, butylmagnesium bromide isobutylmagnesium chloride, pentylmagnesium chloride, heptylmagnesium bromide, octylmagnesium chloride, and the like Cycloalkyl and aryl Grignard reagents such as phenylmagnesium chloride can also be used Alkylmagnesium chlorides are preferred Grignard reagents are often regarded as containing a complex of RMgX or a complex of R 2 Mg and MgX 2 in equilibrium with R 2 Mg and MgX 2 Thus the terms organomagnesium halide and the terms of like import (e g , hydrocarbylmagnesium halide alkylmagnesium halide, etc ) are intended to encompass the materials commonly known as Grignard reagents, whatever their precise chemical structure or configuration may be Upon completion of the above treatment with the Grignard reagent the particulate or powdery product is separated and recovered from the liquid phase by filtration or other suitable solids-liquid physical separation technique such as centrifugation or decantation, and washed with an anhydrous, oxygen-free inert diluent such as hexane Then the product is re-suspended in an anhydrous, oxygen-free inert liquid, such as a paraffinic or cycloparaffinic hydrocarbon, preferably a low boiling hydrocarbon such as hexane, and treated with boron tnhalide, preferably by bubbling boron trifluoride through the suspension at ordinary room temperature and atmospheric pressure for a suitable period of time, e g , up to 5 or 6 hours or more The resultant product can be separated from the liquid phase, if desired, by filtration or other suitable solids-liquid physical separation technique such as centrifugation or decantation, and washed with anhydrous, oxygen-free inert diluent such as hexane. The product can be dried under vacuum at room temperature or slightly elevated temperature (e.g., up to 65°C) and stored under anhydrous oxygen-free conditions such as under a vacuum or under a dry inert gas such as nitrogen or argon. Alternatively the product may be kept in an anhydrous, inert liquid such as a paraffinic or cycloparaffinic hydrocarbon (e.g., hydrogenated alpha-olefin oligomer) which can be used as a medium in which the oligomenzation reaction is to be conducted. If all of the hydroxyl groups of the pendant omega-hydroxyalkyl groups of the initial olefin polymer participate in the reaction with the organomagnesium halide, and if all of the resultant -O-Mg-X groups participate in the reaction with the boron trihalide, the complex of this invention as formed will typically have a magnesium:boron:halide:oxygen atom ratio of 1 :1 :4:1 , respectively. It will be appreciated however that not all of the hydroxyl groups need participate in either of the reactions, that not all of the groups that are reacted with the organomagnesium halide need react with the boron trihalide, and that the boron trihalide can react with some or all of the hydroxyl groups that have not reacted with the organomagnesium halide. Consequently as long as the polymer contains at least one and preferably a plurality of pendant groups containing a moiety composed of one atom of magnesium, one atom of boron, four atoms of halide and one atom of oxygen -- a moiety which for convenience may be depicted as -0-Mg-X-BX 3 — such polymer constitutes a composition of this invention Preferably at least 50%, and more preferably substantially all (i.e., at least 90%) of the initial hydroxyl groups on the polymer will have been converted into such moieties. A few illustrative complexes of this invention are tabulated below with reference to the reactants used for producing them: Oligomenzation Reaction In conducting the oligomenzation process of this invention, oligomenzation is effected by contacting the monomer(s) with a catalytic amount of the catalyst system Typical catalytic amounts fall in the range of about 0.5% to about 30% of the weight of the monomer to be ohgomerized Preferably the catalyst system is used in the range of about 1 % to about 15% of the weight of the 1 -olefin monomer with about 5% to about 10% being most preferred when using catalyst formed without use of organomagnesium halide component, for example formed from olefin polymer with pendant omega-hydroxyalkyl groups and boron tnhalide Oligomenzation temperatures are typically in the range of about 0 to about 80°C, and preferably are in the range of about 20 to about 60°C Thus in conducting the oligomenzation reactions of this invention at least a substantial portion of each individual reaction (e g , at least for one-half of the total reaction period) the oligomenzation reaction is performed at one or more temperatures in the foregoing ranges To ensure intimate contact between the liquid oligomer and heterogeneous catalyst system, the reaction mixture can be agitated during the reaction, or the liquid phase can be passed through a bed of the catalyst system Reaction times will vary depending on the type of product desired and reaction conditions used Generally speaking reaction times will fall in the range of about 0 25 to about 3 hours However, departures from this range are permissible whenever deemed necessary or desirable, and are within the scope of this invention Conventional protic catalyst promoters are not required, but can be used if desired Among promoters that can be used are water, carboxylic acids, mineral acids, alcohols, phenols, carboxylic acid esters and anhydrides, ketones, aldehydes, hydroxy ketones, hydroxy aldehydes, alcohol alkoxylates, and mixtures of any two or more of the foregoing If and when used, the amount of such promoter is typically from about 0 001 to about 0 04 moles per mole of 1 -olefin monomer(s) The promoter can be mixed with the olefin feed or the promoter can be charged separately to the reactor, either entirely at the outset or portionwise as the oligomenzation proceeds In one embodiment of the oligomenzation process of this invention the 1 -olefin or mixture of 1 -olefins, boron tnhalide, and polymer having pendant omega-hydroxyalkyl groups can be charged to the reactor in any suitable sequence Preferably, however, the boron trihalide is introduced directly into a heterogeneous mixture of the 1 -olefin and the solid polymer having pendant omega-hydroxyalkyl groups In another embodiment, the catalyst complex or system formed from polymer having pendant omega-hydroxyalkyl groups organomagnesium halide and boron tnhalide is contacted with the 1 -olefin or mixture of 1 -olefins As noted above, boron trifluoride is the preferred boron tnhalide for use in forming the catalyst system The oligomenzation reaction is typically conducted at about atmospheric pressure, but super-atmospheric pressures can be used, if desired Normally it is unnecessary to exceed pressures of about 100 psig If it is desired to monitor the progress of the reaction, samples of the oligomenzation mixtures can be taken at suitable periods during the course of the reaction and subjected to gas chromatographic (GC) analysis The reaction can be conducted in a single stirred reactor or in a series of reactors Alternatively, the reactor may contain a bed of the catalyst through which the liquid phase is continuously passed or circulated in a closed loop To terminate the oligomenzation reaction, the reaction mixture is simply separated from the heterogeneous catalyst for further processing such as distillation and/or hydrogenation Unreacted olefin can be recovered and recycled As indicated above, because a heterogeneous catalyst is used in the process, the alpha-olefin oligomers can be in a series of two or more separate oligomenzation reactions wherein the same solid polymer component of the catalyst is used over and over again Thus in one of its embodiments this invention provides a process which comprises a) conducting a first or initial reaction of a series of separate oligomenzation reactions by contacting at least one oligomeπzable 1 -olefin having in the range of about 8 to about 20, preferably about 8 to about 14, and most preferably about 8 to about 12 carbon atoms per molecule with a catalyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, and (u) a boron tnhalide, and, optionally, (iii) an organomagnesium halide, whereby the oligomenzation results in a reaction mixture comprising a liquid alpha-olefin oligomer phase and a solids phase comprising solid olefin polymer catalyst residue, b) separating the liquid phase and said solids phase from each other, and c) conducting another such reaction by contacting at least one oiigomenzable 1 -olefin having in the range of about 8 to about 20, preferably about 8 to about 14, and most preferably about 8 to about 12 carbon atoms per molecule with a catalyst system formed from (i) the separated solids phase from the preceding reaction and (u) when the separated solids phase includes solids formed from olefin polymer having pendant omega- hydroxyalkyl groups and boron tnhalide, a fresh charge of boron tnhalide, and when the separated solids phase includes solids formed from olefin polymer having pendant hydroxyalkyl groups and organomagnesium halide and boron tnhalide, an optional fresh charge of boron tnhalide Thus a series of 5, 10, 15 or more successive separate oligomenzation reactions can be performed in which after the end of each reaction the liquid phase and the solids phase are separated from each other, and the solids phase is reused as the catalyst or supplemented with a fresh charge of boron trihalide (preferably boron trifluoride) to form catalyst In either case, such catalyst is used with a fresh charge of an oiigomenzable 1 -olefin in conducting the next oligomenzation reaction of that series of reactions The 1 -olefin can of course be varied from one run to the next Solvents or reaction diluents such as suitable paraffinic or naphthenic oils or paraffinic, cycloparaffinic or aromatic hydrocarbons such as hexane heptane, octane, decane, cyclohexane, toluene, xylene, etc can be employed if desired Excess unreacted olefin can also serve as a diluent Whenever deemed necessary or desirable, the oligomer can be recovered from the liquid phase in which it is formed by conventional procedures such as distillation In order to demonstrate the beneficial results achievable by the practice of this invention, an extended series of batch-type oligomeπzations of 1-octene was carried out using a preferred catalyst system of this invention, namely a system formed from poly(propylene-co-1-hexen-6-ol) ("PP-OH"), boron trifluoride and, in some cases, a hydrocarbon-soluble alkylmagnesium chloride A typical procedure for producing PP-OH involves a) forming B-(5-hexen-1-yl)-9-borobicyclo[3.3.1]nonane ("hexenyl- 9-BBN"), b) copolymenzing the hexenyl-9-BBN with propylene to form poly(propylene-co-1 -hexen-6-yl-9-BBN), and c) oxidizing this boron-containing polyolefin polymer to PP-OH by use of sodium hydroxide and hydrogen peroxide. Although full details for conducting such procedures, including the preparation of hexenyl-9-BBN, are published in patents and technical journals, illustrative procedures are given below It is to be noted that the copolymeπzation described in Example 2 below is performed using a new continuous process that gives superior results as compared to prior batch- type polymerizations. Synthesis details and oligomenzation procedures and results are illustrated by the following examples. EXAMPLE 1 Preparation of Hexenyl-9-BBN A dry 2-liter flask is equipped with a magnetic stirring bar and a connecting tuoe leading to a nitrogen source The flask is thoroughly flushed with nitrogen before the injection inlet is capped with a rubber serum stopple A slight positive pressure of nitrogen is maintained in the flask thereafter The flask is charged via syringe with 190 mL (1.6 mole) of 1 ,5-hexadiene To the stirred diene solution is then added (via syringe) 800 mL of a 0.5 molar 9- BBN-THF solution The reaction is effected with constant stirring at room temperature After a period of three hours, excess 1 ,5-hexadiene and THF solvent are stripped by distillation at reduced pressure. Pure hexenyl-9-BBN is obtained at 130°C and 10 μm. EXAMPLE 2 Copolymenzation of Pro py lene and Hexenyl-9-BBN in a Continuous Reaction In a typical operation, 15 477 g of hexenyl-9-BBN and 200 mL of hexane are placed in an argon filled Parr stirred pressure reactor and sealed Then 12 g of propylene are added under N 2 pressure A slurry of 1 027 g of TιCI 3 and 4 705 g of AIEt 2 CI in 80 mL of toluene are then added under N 2 pressure to catalyze the copolymenzation Additional propylene is added at 30-mιnute intervals with 10, 8, 6 and 5 g of propylene added, respectively After the last monomer charge, the reaction is run for an additional hour before terminating the reaction by injection of 100 mL of isopropyl alcohol The reaction mixture is stirred for an additional 1/2 hour before venting the excess pressure and flushing the polymeric product with additional isopropyl alcohol Some typical results for copolymenzation of propylene and hexenyl- 9-BBN using this continuous polymerization procedure are summarized in Table 1 The process produces copolymer with narrow compositional distribution and higher yield of borane monomer than previously reported procedures Table 1 Run No Mol % Hexenyl-9- Mol % Hexenyl-9-BBN Reaction Yield, % BBN in Feed in Copolymer Tune, hr 1 10 3 5 3 62 2 10 4 2 5 75 3 13 5 0 3 65 4 13 7 8 5 72 EXAMPLE 3 Oxidation of Propylene/Hexenyl-9-BBN Copolymer Propylene/hexenyl-9-BBN copolymer and 700 mL of THF are placed in a 2-liter round bottom flask equipped with septum and stirrer To the resultant non-homogenous slurry is added dropwise a solution of 19 g of NaOH in 100 mL of degassed water. The flask is then cooled to 0°C before slowly adding 87.6 g of degassed 30% H 2 0 2 solution via a double tipped needle. The reaction mixture is allowed to slowly come to room temperature before heating up to 55°C for 6 hours. The PP-OH polymer, poly(propylene- co-1-hexen-6-ol), is then precipitated in water, squeeze dried, and placed in a slurry 500 mL of methanol After 3 hours of vigorous stirring , approximately 75 mL of MeOH is distilled off under N 2 to remove boric acid-methanol azeotrope. The polymer is again precipitated in water , squeeze dried , washed with acetone, and dried under high vacuum at 45°C. Typical properties of the PP-OH polymer formed in this manner and of polypropylene homopolymer made by the same polymerization method (Run No 5) are summarized in Table 2. The PP-OH polymers of Run Nos . 6 and 7 of Table 2 were produced from the hexenyl-9-BBN polymers of Run Nos . 1 and 3 of Table 1 respectively Molecular weights were determined by intrinsic viscosity as measured in a cone/plate viscometer at 135°C in decalin solution. Table 2 Run No. Mol% OH in Melting Heat of Fusion, Intrinsic M_ , g/mol Polymer Pt., β C Viscosity 5 none 163 62.5 2.07 230,000 6 3.5 161 54 1 1.78 183.000 7 5.0 158 44.6 1.71 174.000 Without desiring to be bound by theoretical considerations, the data in Table 2 indicate that the crystal nities, shown by melting point and heat of fusion, of the PP-OH polymers are not much different from that of the polypropylene homopolymer, which is therefore attributed to a tapered structure of the PP- OH polymer Also, the functional groups on the side chains are concentrated at the end of the polymer chain indicating that the polypropylene units are in consecutive sequence to form crystalline phases EXAMPLE 4 Oligomenzation of 1-Octene with PP-OH/Boron Trifluoride Catalyst A series of 15 consecutive oligomenzation reactions was conducted in which the same 0 7 gram sample of poly(propylene-co-1-hexen-6-ol) was recovered by filtration after each run and reused in the next run, a procedure that was repeated over and over again throughout the entire series In each run the PP-OH copolymer and 20 mL of 1-octene were charged to an air-free flask and at the start of each run BF 3 was bubbled into the fresh mixture for 10 minutes while stirring the mixture The slurry was then maintained under the selected reaction conditions for the desired reaction time After each run the o gomer-containing reaction product was filtered to separate the PP-OH copolymer from the liquid oligomer-containing phase The recovered PP-OH and a new 20 mL portion of 1-octene were charged to the flask for the next run Table 3 summarizes the conditions used and the results obtained Table 4 summarizes analytical data concerning the composition of some of the oligomers formed in these runs Table 3 Run No. Reaction Reaction Time, Product Yield, Conversion, % Temp.. β C hr. g 1 20 7.28 50.9 2 20 7.31 51.1 3 20 7.51 52.5 4 20 7.40 51.7 5 20 7.14 49.9 6 20 7.59 53.0 7 20 7.32 51.1 8 20 7.28 50.9 9 20 7.38 51.6 10 20 1.5 9.60 67.1 11 20 7.24 50.6 12 40 9.98 69.8 13 60 13.35 93.3 14 60 0.5 6.91 48.3 15 20 1 .5 10.40 72.7 Table 4 Run No. Dimer, % Trimer, % Tetramer, % Pentamer, % 1 7.8 56.9 18.9 16.4 4 8.1 58.6 17.8 14.5 12 14.5 73.7 9.5 2.3 13 33.4 59.8 6.8 trace 14 35.4 64.0 0.6 - 15 5.8 66.0 17.1 11.1 EXAMPLE 5 Preparation of Catalyst Complex from PP-OH. Grignard Reagent and Boron Trifluoride Poly(propylene-co-1-hexen-6-ol (PP-OH polymer)) containing 3 mole % of hexenol groups, prepared as in Example 3, is ground to a fine powder and vacuum dried for two hours In a dry nitrogen atmosphere, the dried PP- OH polymer (6 grams) is suspended in 40 mL of anhydrous, oxygen-free hexane, and then 50 mmol of butylmagnesium chloride is introduced into the slurry The mixture is kept at room temperature for five hours The resultant complex (PP-OH-Mg-CI) is in the form of powdery solids, and is separated from the liquid phase by filtration through a glass frit and washed three times with anhydrous, oxygen-free hexane The PP-O-Mg-CI powder is then resuspended in 40 mL of dry, oxygen-free hexane, and while continuously stirring the mixture, boron trifluoride is introduced at atmospheric pressure over a three-hour period The solids are again separated by filtration using a glass frit and washed three times with anhydrous, oxygen-free hexane The washed powdery product, PP-O-Mg-CI-BF 3 complex, is dried under vacuum for several hours A sample of a complex formed from the PP-OH Grignard reagent and BF 3 in this manner was subjected to structure characterization and was found to have an Mg B F atom ratio of 1 1 3 EXAMPLE 6 Oligomenzation of 1-Octene with Catalyst Complex from PP-OH. Grignard Reagent and Boron Trifluoride as Catalyst A series of 12 consecutive oligomenzation reactions was conducted in which the same 1 gram sample of PP-0-Mg-CI-BF 3 complex produced as in Example 5 was recovered by filtration after each run in a dry box and reused in the next run, a procedure that was repeated over and over again throughout the entire series In each run powdery solid complex and 10 mL of fresh 1-octene were charged to an air-free 50 mL flask and the mixture was heated up to 60°C for the desired reaction time After each run the ohgomer-containing reaction product was filtered to separate the catalyst complex from the liquid ohgomer-containing phase for use in the next run The separated liquid phase was distilled under vacuum to remove unreacted 1-octene monomer Elemental analysis of the recovered catalyst after the last run of the series showed that almost no change in BF 3 concentration in the catalyst occurred after 12 reaction cycles Table 5 summarizes the conditions used and the results obtained in these 12 runs Table 6 summarizes analytical data concerning the composition of some of the oligomers formed in these runs Table 5 Run No Reaction Reaction Time, Product Yield, Conversion, % Temp., °C hr. g 1 60 2 1.62 22.7 2 60 2 1.84 25.7 3 60 2 1.74 24.3 4 60 2 1 78 24.9 5 60 3 2 45 34.2 6 60 4 3.04 42.5 7 60 2 1.72 24 1 8 60 2 1.85 25.8 9 60 2 1.74 24.3 10 60 2 1.80 25 1 11 60 3 2.29 32.0 12 60 4 3 10 43 3 Table 6 Run No. Dimer, % Trimer, % Tetramer, % Pemamer, % 3 55.5 42.5 2.0 none 8 58.3 40.7 1.0 none The entire disclosure of each and every U S patent and each and every technical publication referred to in any portion of this specification is incorporated herein by reference for all purposes Th i s i nvention is susceptible to considerable variation in its practice Therefore the foregoing description is not intended to limit, and should not be construed as limiting, the invention to the particular exemplifications presented hereinabove Rather, what is intended to be covered is as set forth i n the ensuing claims and the equivalents thereof permitted as a matter of law

Claims: We claim 1 A process of preparing alpha-olefin oligomer which comprises oligomenzing at least one oiigomenzable 1 -olefin having in the range of about 8 to about 20 carbon atoms per molecule by contacting said 1 -olefin with a catalyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, (n) a boron trihalide, and, optionally, (in) an organomagnesium halide 2 A process according to Claim 1 wherein the catalyst system is formed by charging said solid olefin polymer having pendant omega- hydroxyalkyl groups and boron trihalide to said oiigomenzable 1 -olefin 3 A process according to Claim 1 wherein the catalyst system is a complex formed from said solid olefin polymer having pendant omega- hydroxyalkyl groups, said organomagnesium halide and said boron trihalide 4 A process according to any of Claims 1-3 wherein said oiigomenzable 1 -olefin has about 8 to about 14 carbon atoms per molecule and said boron trihalide is boron trifluoride 5 A process according to any of Claims 1-4 wherein said solid olefin polymer is a poly(1-alkene-co-1-alken-u.-ol) polymer in which the alkene units contain 3 to about 10 carbon atoms each and the l-alken-τπ-ol units contain 6 to about 12 carbon atoms each 6 A process according to any of Claims 1 , 2, 4 and 5 wherein the oligomenzation is conducted in a series of two or more separate oligomenzation reactions which comprises a) conducting a first oligomenzation reaction by contacting the oiigomenzable 1 -olefin with a catalyst system formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, and (n) a boron t halide whereby the oligomenzation results in a reaction mixture comprising a liquid alpha-olefin oligomer phase and a solids phase comprising solid olefin polymer catalyst residue, b) separating said liquid phase and said solids phase from each other, and c) conducting another said reaction by contacting oiigomenzable 1 -olefin with a catalyst system formed from (i) said separated solids phase and (n) a fresh charge of a boron trihalide 7 A process according to any of Claims 1 and 3-5 wherein the oligomenzation is conducted in a series of two or more separate oligomenzation reactions which comprises a) conducting a first oligomenzation reaction by contacting the oiigomenzable 1 -olefin with a heterogeneous catalyst complex formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, (n) an organomagnesium halide and (in) a boron tnhalide whereby the oligomenzation results in a reaction mixture compπsing a liquid alpha-olefin oligomer phase and a solids phase comprising solid olefin polymer catalyst residue, b) separating said liquid phase and said solids phase from each other, and c) conducting another said reaction by contacting oiigomenzable 1 -olefin with said solids phase as catalyst 8 A catalyst composition comprising a solid olefin polymer having a linear backbone with at least one pendant group comprising a moiety composed of magnesium, boron, halogen and oxygen in an atomic ratio of 1 1 4 1 and an alkyl group linking said moiety to said backbone 9 A catalyst composition comprising a solid complex formed by a process comprising reacting an organomagnesium halide and a solid olefin polymer having pendant omega hydroxyalkyl groups in an inert, anhydrous liquid medium to form an intermediate product and reacting said product with a boron trihalide in an inert, anhydrous liquid medium 10 A process of preparing alpha-olefin oligomer which comprises oligomenzing at least one oiigomenzable 1 -olefin having in the range of about 8 to about 20 carbon atoms per molecule by contacting said 1 -olefin with a catalyst composition according to Claim 8 or 9

Inventors: CHUNG TZE-CHIANG, DING RUIDONG, SHUBKIN RONALD L, CHUNG, TZE-CHIANG, DING, RUIDONG, SHUBKIN, RONALD, L.
Applicants: AMOCO CORP, AMOCO CORPORATION
Application year: 1996
Main classification: C07C2
IPC codes: B01J31, C07B61, C07C2, C07C11, C10G50