Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/08—Butenes
  • C08F110/10—Isobutene

Definitions

• the invention is directed to a method for producing highly reactive olefin polymers wherein at least 50 mol. % of the polymer chains have terminal double bonds, and a novel polymerization initiating system for accomplishing same.
• IB isobutylene
• PIB polyisobutylene
• dispersants/detergents suitable for use as motor oil and fuel additives.
• These ashless dispersants/detergents can be characterized as oil soluble surfactants with oligoamine end-groups derived from low molecular weight (number average molecular weight (Mn) of from about 500 to about 5000) PIB or polybutenes (copolymers of IB with C4 olefins) having olefinic end groups.
• the "conventional” method uses a C4 mixture and an aluminum ha!ide based catalyst system and produces polybutenes with high tri-substituted olefinic contents. Due to the low reactivity of the tri-substituted olefinic end groups, polybutenes need to be chlorinated to react with ma!eic anhydride to give polybutenylsuccinic anhydride, which is subsequently reacted with oligoalkylenimtnes to yield polybutenylsuccinimide-type ashless dispersant/detergent.
• the other method employs a pure IB feed stream and a BF 3 complex-based catalyst with either alcohols, or ethers in a polymerization reaction run at low temperature, which yields highly reactive PIB (HR PIB) with high exo-olefinic end-group contents.
• HR PIB highly reactive PIB
• PIB exo-olefins readily react with maleic anhydride in a thermal "ene” reaction to produce PIB succinic anhydride and subsequently
• PIB with nearly quantitative exo-ohfm endgroup has been obtained by reacting tert-chloride-terminated PIB (PIB -CI) with strong bases such as potassium teri-butoxide and alkali ethoxides in refluxing tetrahydrofuran (THF) for 20-24 h, (Kennedy, J.P.; Chang, V.S.C.; Smith, R.A.; Ivan, B. Polym. Bull.
• dichloromethane solution not in an apolar, all-hydrocarbon media.
• the catalyst of the catalyst-initiator system of the present invention comprises a Lewis acid catalyst (MR"Y n ) complexed to a Lewis base (B) in an apolar medium.
• the affinity of the Lewis acid for the Lewis base should be such that the Lewis acid can interact at least partially with a conventional cationic initiator (RX) enabling the formation of R + , which initiates cationic polymerization of isobutylene.
• the initially complexed Lewis base should be capable of effecting rapid deprotonation of the growing carbocation chain to form an exo-olefin prior to isomerization of the cationic chain or diffusion of the base into free solution. If the Lewis base does not complex to the Lewis acid, at least initially, deprotonation of the growing carbocation will not be sufficiently rapid relative to isomerization to give the desired high yields of exo- olefin. If the interaction of the Lewis acid and the Lewis base is so strong that it prevents interaction with a conventional initiator, polymerization will be inefficient or not occur at all.
• the Lewis acid or Lewis acid-Lewis base complex must further be capable of interacting with a conventional initiator either in the presence or absence of adventitious water.
• Lewis acid catalysts useful in the practice of the present invention can be represented by the general formula (MR" m Y n ), wherein M is selected from Fe, Ga, Hf, Zr and W; preferably Ga or Fe, more preferably Ga; R" is a hydrocarbyl group, preferably a Ci to C 8 hydrocarbyl group, more preferably a C ⁇ to Cg alkyl group; m is 0 or an integer of 1 to 5, preferably 0 or 1 , more preferably 0; Y is halogen (F, CI, Br), preferably either CI or Br, more preferably CI, and n is an integer of 1 to 6, preferably 3 to 5; with the proviso that m+n is equal to the valency of M.
• M is selected from Fe, Ga, Hf, Zr and W; preferably Ga or Fe, more preferably Ga
• R" is a hydrocarbyl group, preferably a Ci to C 8 hydrocarbyl group, more preferably a C ⁇ to
• hydrocarbyl means a chemical group of a compound that contains hydrogen and carbon atoms and that is bonded to the remainder of the compound directly via a carbon atom.
• the group may contain one or more atoms other than carbon and hydrogen (“hetero atoms”) provided they do not affect the essentially hydrocarbyl nature of the group.
• the Lewis base (B) is selected from oxygen- and/or sulfur-containing nuc!eophiles, such as ethers, alcohols, ketones, aldehydes and esters, and sulfur- containing nucleophiles such as thioethers and thioketones.
• Lewis bases include acyclic dihydrocarbyl ethers, wherein each hydrocarbyl group is independently selected from Ci to Cj 2 hydrocarbyl, cyclic ethers having a 5 to 7 membered cyclic group, dihydrocarbyl ketones, wherein each hydrocarbyl group is independently selected from C
• the hydrocarbyl groups of the above Lewis bases are preferably alkyl groups and are more preferably Ci to C 4 alkyl.
• the hydrocarbyl groups and cyclic aliphatic groups of the above Lewis bases may each independently be substituted with a heteroatom or a heteroatom-containing moiety and may further be substituted with other substituent groups that do not interfere significantly with the ability of such compounds to function as a Lewis base (e.g., Ci to C "lower alkyl" groups).
• an “initiator” is defined as a compound that can initiate polymerization, in the presence or absence of adventitious water and in the presence of a proton trap.
• the initiator of the present invention (RX) comprises a hydrocarbyl R group wherein the carbon linking group R to X is tertiary, benzylic or allylic, which hydrocarbyl group can form a stable carbocation (e.g., t-butyl + ), and an X group, which is a halogen.
• the polymerization medium must be a substantially or completely apolar medium, such as a mixture of hexanes or saturated and unsaturated C 4 hydrocarbons, in the polymerization process of the present invention, the feedstock may be pure isobutylene or a mixed C 4 hydrocarbyl feedstock containing isobutylene, such as a C 4 cut resulting from the thermal or catalytic cracking operation of, for example, naphtha.
• suitable feedstocks will typically contain at least 10%, and up to 100% isobutylene, by mass, based on the total mass of the feed.
• C 4 cuts suitable for use as feedstocks that are of industrial importance typically will contain between about 5% and about 50% butene-1, between about 2% and about 40% butene-2, between about 2% and about 60% iso- butane, between about 2% and about 20% n-butane, and up to about 0.5% butadiene, all percentages being by mass, based on the total feed mass.
• Feedstocks containing isobutylene may also contain other non-C 4 polymerizable olefin monomers in minor amounts, e.g., typically less than 25%, preferably less than about 10%, and most preferably less than 5%, such as propadiene, propylene and C 5 olefins.
• the C 4 cut may be purified by conventional means to remove water, polar impurities and dienes.
• polybutene as employed herein is intended to include not only homopolymers of isobutylene, but also copolymers of isobutylene and one or more other C 4 polymerizable monomers of conventional C 4 cuts as well as non-C 4 ethylenically unsaturated olefin monomers containing 5 carbon atoms, provided such copolymers contain typically at least 50%, preferably at least 65%, and most preferably at least 80%. isobutylene units, by mass, based on the polymer number average molecular weight (Mn ).
• the Lewis acid and Lewis base can be complexed by, for example, dissolving the Lewis acid in a solvent (e.g., dichloromethane or 1, 2-dichloroethane) to form a solution and then adding the Lewis base to the solution, while the solution is stirred.
• a solvent e.g., dichloromethane or 1, 2-dichloroethane
• the complex may be added to the polymerization medium with the solvent;
• the solvent may be removed prior to the addition of the complex to the polymerization medium.
• the molar ratio of Lewis acid to Lewis base in the complex will typically be maintained within a range of from about 1 :0.5 to about 1 :2, preferably from about 1 :0.7 to about 1 :1.5, more preferably from about 1 :0.8 to about 1 :1.2 , such as from about 1 :0.9 to about 1 :1.1 or 1 :1.
• the amount of the Lewis acid-Lewis base complex employed in the process of the present invention can be controlled, in conjunction with the concentration of initiator and monomer, reaction time and temperature, to achieve the target Mn of the polybutene polymer product, the conversion of butene and yield of polybutene.
• the Lewis acid-Lewis base complex is typically employed in an amount sufficient to contact the butene monomer in a liquid phase reaction mixture at a concentration of millimoles of Lewis acid-Lewis base complex per liter of reaction mixture of from about 1 mM to about 200 mM, preferably from about 5 mM to about 100 mM, and more preferably from about 10 mM to about 50 mM, such as from about 10 mM to about 30 mM.
• the initiator will typically be employed in an amount sufficient to contact the butene monomer in a liquid phase reaction mixture at a concentration of millimoles of initiator per liter of medium, and independent from the amount of Lewis acid-Lewis base complex, of from about 1 mM to about 200 mM, preferably from about 5 mM to about 100 mM, and more preferably from about 10 mM to about 50 mM, such as from about 10 mM to about 30 mM.
• the polymerization reaction can be conducted batch-wise, semi-continuously, or continuously. On an industrial scale, the polymerization reaction is preferably conducted continuously.
• Conventional reactors such as tubular reactors, tube-bundle reactors or loop reactors, ie, tube or tube-bundle reactors with continuous circulation of the reaction material, may be used.
• the polymerization reaction is conducted in the liquid phase to induce linear or chain-type polymerization, as opposed to ring or branch formation.
• a feed that is gaseous under ambient temperature
• Typical C 4 cuts comprising the feed are liquid under pressure and do not require a solvent or diluent.
• Typical diluents suitable for use with the process include C 3 to C 6 alkanes, such as propane, butane, pentane, isobutane and the like.
• the Lewis acid-Lewis base complex is typically introduced into the reactor as a liquid partially or completely dissolved in a solvent, or as a solid. Polymerization is preferably conducted at a pressure sufficient to maintain the C 4 feed in a liquid state at the reaction temperature, or at higher pressures.
• the initiator may be introduced to the monomer feed or the reaction mixture in liquid form together with the Lewis acid- Lewis base complex or, preferably, is introduced to the monomer feed or the reaction mixture in liquid form by a line separate from the Lewis acid-Lewis base complex addition line.
• the liquid phase reaction mixture temperature is controlled by conventional means to be typically from about -30°C to about +50°C, preferably from about -10°C to about +30°C, more preferably from 0°C to about +20°C, such as from 0°C to about +10°C.
• the residence time of the butene to be polymerized may be from about 5 seconds to several hours, but will typically be from about 1 to about 300 minutes, such as 2 to about 120 minutes, preferably from about 5 to about 60 minutes.
• turbulent flow of the reactor contents can be generated by mixing, or with suitable baffles, such as baffle plates or oscillating baffles, or by dimensioning the reactor tube cross sections so that a suitable flow velocity is established.
• the process of the present invention is typically conducted in a manner achieving an isobutylene conversion in the range of from about 20% up to about 100%, preferably from about 50% to about 100%, and more preferably from about 70% to about 100%.
• the combined use of temperature control and catalyst feed rate permits formation of polybutenes having a Mn of from about 400 Daltons to about 4000 Daltons, preferably from about 700 Daltons to about 3000 Daltons, more preferably from about 1000 Daltons to about 2500 Daltons; a molecular weight distribution (MWD) of typically from about 1.1 to about 4.0, preferably from about 1.5 to about 3.0, an exo-oiefin content of greater than 50 mol. %, preferably greater than 60 mol. %, more preferably greater than 70 mol.
• % such as from about 80 mol. % to about 95 mol. %; a tetrasubstituted olefin content of less than about 20 mol. %, such as less than about 15 mol. %, preferably less than about 10 mol. %, more preferably less than about 5 mol. %; and a chlorine content of less than about 10 mol. %, such as less than about 5 moi. %, preferably less than about 2 mol. %, more preferably less than about 1 moi. %, based on the total moles of polymer.
• the polymer product can be discharged from the reactor and passed into a medium that deactivates the polymerization catalyst and terminates the polymerization.
• Suitable deactivation media include water, amines, alcohols and caustics.
• the polyisobutylene product can then be separated by distilling off the remaining C 4 hydrocarbons and low molecular weight oligomers. Preferably residual amounts of catalyst are removed, usually by washing with water or caustic.
• LA (3.9 mmol) was first dissolved in 3.36 ml of dichloromethane in a 20 ml vial equipped with a screw top with a septum. The vial was cooled down to 0°C. to form a 1M complex. LB (3.9 mmol) was then added drop wise for 1 minute, while the solution was stirred. The solution was kept at +25 °C and it was used within 1 hour of preparation.
• Polymerization was performed in a dry N 2 atmosphere MBraun 150-M glove box (Innovative Technology Inc., Newburyport, MA). Yields were determined gravimetrically. Number average molecular weights ( Mn) and polydispersity indices (PDI) were determined by size exclusion chromatography. The distribution of end- groups was determined ⁇ by ⁇ NMR. The amount of unreacted chlorinated PIB (PIB- CI), which is one indicator of whether the reaction can be driven further to completion, was determined by proton NMR spectroscopy.
• Mn Number average molecular weights
• PDI polydispersity indices
• AICI3 polymerizes IB in hexanes without added initiator. Initiation is by adventitious water which is inefficient and the amount of which is difficult to control. Monomer conversion was low and polydispersity was high.
• IB, hexanes, CumOH, and DTBP were premixed in a 75 ml culture tube, equipped with a screw top with a septum.
• the LA.LB complex was added last.
• the polymerization was quenched with excess of aqueous NH4OH.
• Example 5 Comparing Example 5 to Example 4 demonstrates that TMPC does not initiate t le polymerization when A1C1 3 is the LA. Conversion, Mn and end-group distribution remained substantially the same.
• IB, hexanes, TMPC1, and DTBP were premixed in a 75 ml culture tube, equipped with a screw top with a septum.
• the LA.LB complex was added last.
• the polymerization was quenched with excess of aqueous Nl3 ⁇ 4OH. Monomer conversion: 0 %
• IB, hexanes, and tBuOH were premixed in a 75 ml culture tube, equipped with a screw top with a septum.
• the LA.LB complex was added last.
• the polymerization was quenched with excess of methanol.
• EXAMPLE 8 (Comparative) Polymerization of IB was performed as in Example 6, except that cumy] chloride (CumCl) was used instead of TMPC1, and AlCI 3 .diisopropyl ether was used instead AlCl3.diisobutyi ether.
• IB, hexanes, and TMPC1 were premixed in a.75 ml culture tube, equipped with a screw top with a septum. Addition of the LA.LB complex started the
• the polymerization was quenched with excess of aqueous NH 4 OH.
• the LA GaCl 3 (0.02 M) was used to polymerize IB (1 M) in hexanes in the presence of TMPCl (0.02 M) and isopropyl ether (0.02 M) at 0'C for 20 minutes.
• IB, hexanes, isopropyl ether, and TMPCl were premixed in a 75 ml culture tube, equipped with a screw top with a septum.
• Addition of 1M solution of GaCl 3 in hexane (0.02 M) started the polymerization.
• the polymerization was quenched with excess of aqueous NH 4 OH.
• Polymerization of IB was performed as in Example 12 except that polymerization time was increased to 40 minutes.
• Example 10 Yield is reduced but not eliminated by DTBP. MW and exo-olefin content is maintained. Compare to Example 6 with A1C1 3 where no conversion was achieved in the presence of DTBP.
• Ketone is effective as the Lewis base with comparable MW and exo-olefin content, but lower conversion.
• FeCl 3 is an effective Lewis acid catalyst with higher exo- olefin content at similar MW, but lower conversion.
• IB, hexanes, and tBuCl were premixed in a 75 ml culture tube, equipped with a screw top with a septum. Addition of the LA.LB complex started the polymerization. The polymerization was quenched with excess of aqueous NH 4 OH.

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