Patent Description:
Common methods to polymerize isobutylene and form polyisobutylene (PIB) with one carbon-carbon double bond include using Lewis acid catalysts, such as boron trifluoride (BF<NUM>) and aluminum trichloride (AlCl<NUM>). The double bond can be located at the end of the polymer chain (e.g., alpha vinylidenes) or it can be located more internal in the chain as in beta vinylidene or other trisubstituted olefin isomers, or tetra substituted olefin isomers. PIB containing a high proportion of alpha vinylidene olefin isomers is referred to as highly reactive polyisobutylene (HR-PIB). Such polymer molecules are more reactive in subsequent derivatization reactions to produce derivatives such as fuel and lubricant additives than other types of PIB.

Conventional AlCl<NUM> catalysts typically produce PIB that has olefin isomers other than alpha vinylidene. These PIB products are known as conventional PIB and are significantly less reactive in derivatization reactions.

Catalyst complexes (such as liquid BF<NUM>/complexing agent) have been developed to produce HR-PIB. See <CIT>; <CIT>; <CIT>; <CIT>; and International Publication No. <CIT>. However, many liquid BF<NUM>/complexing agents are unstable and must be prepared in situ, requiring the handling of highly toxic BF<NUM> gas on site. The liquid BF<NUM>/complexing agents must also be removed post-reaction by extensive water washing processes which are highly complex and generate large amounts of waste water. Moreover, the waste water contains fluoride salts that require disposal.

<CIT> and <CIT> describe polyisobutylene compositions, and methods and catalyst systems to produce such compositions. The catalyst system is a solid BF<NUM>/alcohol catalyst complex on a metal oxide support material of gamma alumina beads or spheres, and the catalyst system is used in a fixed bed reactor. The PIB products made include internal vinylidene isomers and alpha vinylidene isomers, such that the alpha vinylidene olefin isomers in these compositions are significantly less than <NUM> wt%.

Publication. No. <CIT> discloses a catalyst system for heterogeneous catalysis of organic compound conversion reactions including isobutylene polymerization to form polyisobutylene.

<CIT> discloses a method of preparing alumina with pores and reacting BF<NUM>/methanol complexes with the porous alumina. The BF<NUM>/methanol/alumina catalyst system produces PIB compositions in which the alpha vinylidene isomer content is significantly less than <NUM> wt%.

Other references that describe conventional PIB processes and catalysts include: <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; and International Publication No. <CIT>.

<CIT> describes fluorinated transition metal catalysts and methods of forming the same.

There exists a need for an improved process to produce HR-PIB compositions having an alpha vinylidene olefin isomer content greater than about <NUM>% and catalyst for producing such materials.

In an aspect, a catalyst system is provided. The catalyst system includes a support material selected from the group consisting of Al<NUM>O<NUM>, ZrO<NUM>, TiO<NUM>, SnO<NUM>, CeO<NUM>, SiO<NUM>, SiO<NUM>/Al<NUM>O<NUM>, and combinations thereof, the support material having an Al<NUM>O<NUM> content between <NUM> wt% and <NUM> wt% based on the total weight of the support material; and BF<NUM>, wherein the concentration of BF<NUM> is greater than <NUM> wt% based on the total weight of the catalyst system.

In an aspect, a method of forming a polymer composition is provided. The method includes contacting isobutylene with the catalyst system as herein described; and forming the polymer composition.

In an aspect, a method of forming the catalyst system as herein described is provided. The method includes calcining a support material at a temperature of <NUM> to <NUM>, the support material selected from the group consisting of Al<NUM>O<NUM>, ZrO<NUM>, TiO<NUM>, SnO<NUM>, CeO<NUM>, SiO<NUM>, SiO<NUM>/Al<NUM>O<NUM>, and combinations thereof, the support material having an Al<NUM>O<NUM> content between <NUM> wt% and <NUM> wt% based on the total weight of the support material; and forming the catalyst system by adding to the support material a mixture comprising BF<NUM>.

It is to be noted, however, that the appended drawings illustrate only exemplary embodiments and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments.

The present disclosure relates to catalyst compositions and processes to make polyisobutylenes (PIB), and particularly highly reactive polyisobutylene (HR-PIB). The present disclosure also relates to PIB compositions, particularly HR-PIB compositions.

For purposes of this disclosure, HR-PIB is a composition containing greater than about <NUM>% alpha vinylidene olefin isomer. The HR-PIB compositions can contain additional olefin isomers including beta vinylidene olefin isomer, other trisubstituted olefin isomers, internal vinylidenes, and tetrasubstituted olefin isomers. HR-PIB is termed highly reactive because of its increased reactivity in derivatization reactions, such as reactions with maleic anhydride to produce polyisobutenylsuccinic anhydride (PIBSA) to form precursors useful for fuel and lubricant additives.

For purposes of this application, molecular structures may be represented by bond-line structure (also known as skeletal structure) in which the position of carbon and hydrogen atoms may be implied.

For purposes of this application, an alpha vinylidene olefin isomer (also referred to as α-vinylidene) has the following structure:
<CHM>.

For purposes of this application, a beta vinylidene olefin isomer (also referred to as β-vinylidene) has the following structure:
<CHM>.

For purposes of this application, an internal disubstituted vinylidene olefin isomer includes the following structure:
<CHM>.

Other internal vinylidenes are possible, including where the position of the olefin in the polyisobutylene is such that the olefin is disubstituted and not at the end of the carbon chain. For purposes of this application other trisubstituted olefin isomers and tetrasubstituted olefin isomers may be produced in the polymerizations described herein.

As used herein, an "olefin," alternatively referred to as "alkene," is a linear, branched, or cyclic compound of carbon and hydrogen having at least one carbon-carbon double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the polymer or copolymer has polymer molecules that have at least one olefin bond.

A "polymer" has two or more of the same or different monomer ("mer") units bonded together in a single polymer molecule, or a collection of such polymer molecules. A "homopolymer" is a polymer having mer units that are the same. A "copolymer" is a polymer having two or more mer units that are different from each other. "Different" as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically.

As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, wt% is weight percent, and mol% is mole percent. Unless otherwise noted, all molecular weight units (e.g., Mw and Mn) are daltons (Da).

As used herein, a "catalyst" includes a single catalyst, or multiple catalysts with each catalyst being conformational isomers or configurational isomers. Conformational isomers include, for example, conformers and rotamers. Configurational isomers include, for example, stereoisomers.

The term "catalyst complex" refers to a complex of a catalyst and a complexing agent. Catalyst complex includes a single catalyst complex or multiple catalyst complexes.

The term "catalyst system" refers to a composition comprising a catalyst and a support material. Catalyst system also refers to a composition comprising a catalyst complex with a support material. When catalyst systems are described (including by structure or formula) as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the form that reacts with the polymer precursors to produce polymers may be a reactive form that results directly from proper use of the catalyst system.

Furthermore, catalysts of the present disclosure (which may be represented by a formula and/or a structure) are intended to embrace ionic, reactive, or reaction product forms of the catalysts in addition to the neutral forms of the catalysts. Furthermore, complexing agents of the present disclosure (which may be represented by a formula and/or a structure) are intended to embrace ionic, reactive, or reaction product forms of the complexing agents in addition to neutral forms of the complexing agents. Moreover, catalyst systems of the present disclosure (which may be represented by a formula and/or a structure) are intended to embrace ionic, reactive, or reaction product forms of the catalyst systems in addition to neutral forms of the catalyst systems.

As used herein, composition includes components of the composition and/or reaction products thereof.

A catalyst system, when made, sold, or used includes about <NUM>% to about <NUM>% of BF<NUM>.

Unless otherwise indicated, the term "substituted" generally refers to a hydrogen of the substituted species being (or has been) replaced with a different atom or group of atoms.

The following abbreviations may be used herein: Me is methyl; Et is ethyl; Pr is propyl; nPr is normal propyl; iPr is isopropyl; Bu is butyl; nBu is normal butyl; iBu is isobutyl; sBu is sec-butyl; tBu is tert-butyl; THF (also referred to as thf) is tetrahydrofuran; MeOH is methanol; MTBE (also referred to as mtbe) is methyl tert-butyl ether; RT is room temperature (and is between about <NUM> and about <NUM> unless otherwise indicated).

The terms "hydrocarbyl radical," "hydrocarbyl," "hydrocarbyl group," "alkyl radical," "alkyl," and "alkyl group" may be used herein, and if used, are used interchangeably. Likewise, the terms "group," "radical," and "substituent" are also used interchangeably in this document, referring only to chemical groups that are attached to other chemical structures, implying nothing about the state, structure, charge, or condition of such groups when not attached to other chemical structures. For purposes of this disclosure, "hydrocarbyl radical" refers to C<NUM>-C<NUM> radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, benzyl, and their substituted analogues. Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one halogen (such as Br, Cl, F or I) or at least one functional group such as C(O)R*, C(O)NR*<NUM>, C(O)OR*, NR*<NUM>, OR*, SeR*, TeR*, PR*<NUM>, AsR*<NUM>, SbR*<NUM>, SR*, BR*<NUM>, SiR*<NUM>, GeR*<NUM>, SnR*<NUM>, and PbR*<NUM> (where R* is independently a hydrogen or hydrocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.

The term "alkenyl" may be used herein, and if used, refers to a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more double bonds. These alkenyl radicals may be optionally substituted.

The term "aryl" or "aryl group" may be used herein, and if used, includes a C<NUM>-C<NUM> aromatic ring, such as a six carbon aromatic ring, and the substituted variants thereof, including phenyl, <NUM>-methyl-phenyl, xylyl, <NUM>-bromo-xylyl. Likewise heteroaryl refers to an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, for example, N, O, or S. As used herein, the term "aromatic" also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise the term aromatic also refers to substituted aromatics.

The term "Ring structure" may be used herein, and if used, refers to atoms bonded together in one or more cyclic arrangements.

The term "ring atom" may be used herein, and if used, refers to an atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring atoms and tetrahydrofuran has <NUM> ring atoms.

The term "heterocyclic ring" may be used herein, and if used, refers to a ring having a heteroatom in the ring structure as opposed to a heteroatom-substituted ring where a hydrogen on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocyclic ring and <NUM>-N,N-dimethylamino-phenyl is a heteroatom-substituted ring.

As used herein, the term "aromatic" also refers to pseudoaromatic heterocycles which are heterocyclic structures that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise, the term aromatic also refers to substituted aromatics.

The term "continuous" refers to a system that operates without interruption or cessation while performing a particular process for which the system is designed. For example, a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn during a polymerization process.

A solution polymerization refers to a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an unreactive solvent or polymerizable compounds (including polymer precursors) or their blends.

A bulk polymerization refers to a polymerization process in which the precursors being polymerized are used as a solvent or diluent using little or no unreactive solvent as a solvent or diluent. A small fraction of unreactive solvent might be used as a carrier for a catalyst system. A bulk polymerization system contains less than about <NUM> wt% of unreactive solvent or diluent, for example, less than about <NUM> wt%, less than about <NUM> wt%, or about <NUM> wt%.

As used herein the term "slurry polymerization process" refers to a polymerization process where a supported catalyst is employed and polymer precursors are polymerized on the supported catalyst particles.

"Homopolymerization" would produce a polymer made from one type of polymerizable compounds (including polymer precursors), whereas "copolymerization" would produce polymers with more than one polymerizable compound type.

Catalysts for the polymerization processes described herein comprise BF<NUM>. The catalysts described herein are capable of forming polyisobutylenes (PIB) and particularly HR-PIBs.

The catalyst complexes described herein, like the Lewis acid catalysts, are capable of forming PIB and particularly HR-PIBs. Some of the disclosed catalyst complexes comprise BF<NUM> and a complexing agent.

In some embodiments, the Lewis acid catalyst is complexed with a complexing agent. Alternately, the Lewis acid catalyst can be used without a complexing agent. The catalyst systems described herein are solids, for example powders. The solid catalyst systems described herein are formed by contacting the Lewis acid catalyst alone (e.g., BF<NUM> gas) with a support material, or by complexing the Lewis acid catalyst complex (e.g., BF<NUM>/complexing agent) with a support material.

Complexing agents include linear, branched, cyclic, heterocyclic (for example, tetrahydrofuran and tetrahydropyran), aryl (such as phenol and benzyl alcohol), and heteroaryl compounds.

In some embodiments, the complexing agent is a compound that has a lone pair of electrons (such as oxygen containing compounds and nitrogen containing compounds). Nitrogen containing compounds include amines, polyamines (such as ethylene diamine), amides, polyamides, amino acids, polyamino acids, and polyaminocarboxylic acids such as ethylenediamine tetracetic acid (EDTA). In some embodiments, the nitrogen containing compound is an unsubstituted C<NUM> to C<NUM> amine (such as alkylamines, including methyl amine, ethyl amine, propyl amine, decyl amine and lauryl amine), a substituted C<NUM> to C<NUM> amine, including alkanol amines (such as ethanol amine, diethanol amine, triethanol amine, propanol amine, diethylethanol amine), an unsubstituted C<NUM> to C<NUM> polyamine (such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and heavy polyamine X (HPA X)), a substituted C<NUM> to C<NUM> polyamine, an unsubstituted C<NUM> to C<NUM> amide (such as formamide, acetamide, <NUM>-propenamide, and benzamide), a substituted C<NUM> to C<NUM> amide (such as N,N-dimethylformamide (DMF), N,N-dimethypropanamide, N-methylacetamide, and N-phenylacetamide), aliphatic polyamides (such as Nylon <NUM> and Nylon <NUM>), polyphthalamides (such as hexamethylenediamine terepthalate), aramids (such as Kevlar and Nomex), an amino acid (such as the <NUM> standard amino acids, for example aspartic acid and glycine), a polyamino acid (such as poly(hydroxypropyl-L-glutamine) and poly-L-leucine), polyaminocarboxylic acids.

Oxygen containing compounds (also known as oxygenates) that may be used include alcohols, ethers, ketones, aldehydes, and carboxylic acids. In some cases, the complexing agent is an oxygen containing compound such as an alcohol or an ether (symmetrical or asymmetrical). In other cases, the complexing agent is a C<NUM> to C<NUM> unsubstituted alcohol, a C<NUM> to C<NUM> substituted alcohol, a C<NUM> to C<NUM> unsubstituted ether, or a C<NUM> to C<NUM> substituted ether.

In some cases, the complexing agent is an alcohol that lacks a beta hydrogen such as methanol, <NUM>,<NUM>-dimethyl alcohols (for example, neopentyl alcohol, <NUM>,<NUM>-dimethylbutanol, <NUM>,<NUM>-dimethylpentanol, and <NUM>,<NUM>-dimethylhexanol), benzyl alcohol, and ring-substituted benzyl alcohols.

In some embodiments, the complexing agent contains more than one oxygen containing group per molecule, for example, glycols (substituted or unsubstituted) and polyols (substituted or unsubstituted), for example wherein each hydroxyl is in a primary position, or for example, a C<NUM> to C<NUM> glycol (substituted or unsubstituted) such as ethylene glycol, <NUM>,<NUM>-butanediol, trimethylolethane (<NUM>-(hydroxymethyl)-<NUM>-methylpropane-<NUM>,<NUM>-diol; CSH<NUM>O<NUM>), trimethylolpropane (<NUM>-(hydroxymethyl)-<NUM>-ethylpropane-<NUM>,<NUM>-diol; C<NUM>H<NUM>O<NUM>), pentaerythritol (<NUM>,<NUM>-bis(hydroxymethyl)propane-<NUM>,<NUM>-diol; C<NUM>H<NUM>O<NUM>), and tris(hydroxymethyl)aminomethane (C<NUM>H<NUM>NO<NUM>).

In one embodiment, the complexing agent is methanol, ethanol, isopropanol (also known as isopropyl alcohol), n-propanol (also known as propan-<NUM>-ol), neopentyl alcohol (also known as <NUM>,<NUM>-dimethyl-<NUM>-propanol and neopentanol), dimethyl ether, diethyl ether, diisopropyl ether, diisobutyl ether, di-tert-butyl ether, methyl tert-butyl ether (MTBE), or ethylene glycol. In some cases, the oxygen containing compound is methanol.

In some embodiments, the catalyst complex (e.g., the BF<NUM>/complexing agent) is formed by passing BF<NUM> gas through the pure anhydrous oxygen containing compound (or nitrogen containing compound) at a rate that allows the BF<NUM> to be efficiently absorbed.

In some embodiments, the mole ratio of complexing agent to BF<NUM> is between about <NUM> and about <NUM> in the catalyst complex. In other embodiments, the mole ratio is between about <NUM> and about <NUM>. In some cases, the mole ratio is between about <NUM> and <NUM>. In other cases, the mole ratio is between about <NUM> and about <NUM>, for example between about <NUM> and about <NUM>. In some embodiments, the mole ratio is between about <NUM> and about <NUM>, for example, about <NUM>.

The catalyst system comprises an unreactive support material. The support materials for the catalyst and/or catalyst complex include any support material that forms a stable adduct with BF<NUM> selected from the group consisting of Al<NUM>O<NUM>, ZrO<NUM>, TiO<NUM>, SnO<NUM>, CeO<NUM>, SiO<NUM>, SiO<NUM>/Al<NUM>O<NUM>, and combinations thereof. In an embodiment, the support material is a porous support material, comprising inorganic oxides. Other suitable support materials are the metal oxides doped with rare earth metals or rare earth metals themselves or combinations of both.

In some embodiments, the support material is an inorganic oxide in a finely divided form, such as a powder. Suitable inorganic oxide materials for use in catalyst systems herein include metal oxides of Group IIIA, Group IVA, and Group IVB of the Periodic Table of the Elements, such as alumina, silica, and titania, and mixtures thereof. Inorganic oxides may be employed either alone or in combination with the silica or alumina including titania and zirconia. Combinations of the support materials may be used, for example, silica-alumina, and silica-titania. Support materials include Al<NUM>O<NUM>, ZrO<NUM>, TiO<NUM>, SnO<NUM>, CeO<NUM>, SiO<NUM>, SiO<NUM>/Al<NUM>O<NUM>, and combinations thereof. The support materials may include SiO<NUM>, Al<NUM>O<NUM>, SiO<NUM>/Al<NUM>O<NUM>, or combinations thereof.

In some embodiments, the support material has one or more of the following properties:.

In some embodiments, the support material is a high surface area, amorphous silica (for example, the surface area is about <NUM><NUM>/g and the pore volume is about <NUM><NUM>/gm).

Other support materials include the following: catalyst substrate spheres (CSS) <NUM>™ gamma-alumina spheres (CSS <NUM>™ γ-Al<NUM>O<NUM>) which can be purchased from BASF Corporation; ALS <NUM>™ SiO<NUM>/Al<NUM>O<NUM> (silica-alumina) support material which can be purchased from Pacific Industrial Development Corporation; and ALS <NUM>™ SiO<NUM>/Al<NUM>O<NUM> (silica-alumina) support material which can be purchased from Pacific Industrial Development Corporation. Table <NUM> shows the physical properties of these support materials prior to heating, calcining, and complexing with the catalyst and/or catalyst complexes.

The support material should be dry, that is, free (or essentially free) of absorbed water before addition of the catalyst or the catalyst complex. Drying of the support material can be effected by heating or calcining at a temperature of at least about <NUM> (for example, between about <NUM> and about <NUM>, such as between about <NUM> and <NUM>, between about <NUM> and <NUM>, between about <NUM> and about <NUM>, or between about <NUM> and about <NUM>); and for a time of between about <NUM> minute and about <NUM> hours (for example, between about <NUM> minute and about <NUM> hours, such as between about <NUM> minute and about <NUM> hours, or between about <NUM> hours and about <NUM> hours, such as about <NUM> hours, about <NUM> hours, <NUM> hours, or about <NUM> hour).

In some embodiments, the support material is calcined when first manufactured and/or recalcined as received. The calcined support material is then contacted with at least one of a mixture comprising BF<NUM> and a mixture comprising BF<NUM> and complexing agent.

Other support materials that can be used include organic supports that are a solid or that forms a solid when complexed with BF<NUM> and/or BF<NUM> and complexing agent. This organic support can be used in combination with the inorganic oxide support material. While not wishing to be bound by theory, it is believed that the organic support, like an inorganic oxide support, provides active sites for the BF<NUM> and/or BF<NUM> and complexing agent. In some embodiments, this support can be any solid organic complexing agent containing O or N functionality (or any functionality) that is capable of supporting BF<NUM> or BF<NUM> complexes. Alternately, the support can be an organic complexing agent containing O or N functionality (or any functionality) that forms a solid when complexed BF<NUM> or BF<NUM> complexes. Examples of such complexing agents that act as supports include ion exchange resins such as anionic exchange resins and cationic exchanges resins, including strongly acidic cation exchange resins, weakly acidic cation exchange resins, strongly basic anionic exchange resins, and weakly basic anionic exchange resins. For example, Amberlyst™ and Amberlite™ resins (such as Amberlyst <NUM> sulfonic acid and Amberlite IRA <NUM> weak base (amine) resin) commercially available from Dow and Sigma Aldrich. may be used as the support. The ion exchange resins may be used with or without calcining (or otherwise pretreated or heated). Dehydration (or otherwise heating) temperatures of the ion exchange resins include temperatures greater than about <NUM> (such as between about <NUM> and about <NUM>, for example between about <NUM> and about <NUM>, such as about <NUM>); and for a time of between about <NUM> minute and about <NUM> hours (for example, between about <NUM> minute and about <NUM> hours, such as between about <NUM> minute and about <NUM> hours, or between about <NUM> hours and about <NUM> hours, such as about <NUM> hours, about <NUM> hours, <NUM> hours, or about <NUM> hours).

Some embodiments described herein are catalyst systems. A catalyst system can be made from any catalyst described herein, any support material described herein, any complexing agent described herein, and/or any catalyst complex described herein.

A catalyst system includes BF<NUM> and a support material selected from the group consisting of Al<NUM>O<NUM>, ZrO<NUM>, TiO<NUM>, SnO<NUM>, CeO<NUM>, SiO<NUM>, SiO<NUM>/Al<NUM>O<NUM>, and combinations thereof, wherein the concentration of BF<NUM> is greater than about <NUM>% by weight (for example, greater than about <NUM> wt%, or greater than about <NUM> wt%), based on the total weight of the catalyst system (i.e., BF<NUM> plus the support material).

Also disclosed is a catalyst system including BF<NUM> and an organic support material that is an ion exchange resin (i.e., an anionic exchange resin, a cationic exchanges resins (such as Amberlyst™ and Amberlite™ resins), and/or combinations thereof), wherein the concentration of BF<NUM> is greater than about <NUM>% by weight (such as about <NUM> wt%), based on the total weight of the catalyst system (i.e., BF<NUM> plus the support material).

In still other embodiments, a catalyst system includes a combination of inorganic oxide (i.e., Al<NUM>O<NUM>, ZrO<NUM>, TiO<NUM>, SnO<NUM>, CeO<NUM>, SiO<NUM>, SiO<NUM>/Al<NUM>O<NUM>, and combinations thereof) and organic support (i.e., ion exchange resins, such as anionic and cationic exchange resins for example Amberlyst™ and Amberlite™ resins).

The catalyst system can further include a complexing agent, wherein the concentration of BF<NUM> is greater than about <NUM>% by weight (for example, greater than about <NUM> wt%, or greater than about <NUM> wt%), based on the total weight of the catalyst system (i.e., BF<NUM> plus the complexing agent plus the support material). The actual concentration of F or B in the catalyst complex/support material depends on the complexing agent used.

In embodiments where the catalyst system is formed by adding to the support material a mixture comprising BF<NUM> and a complexing agent, the mole ratio of complexing agent to BF<NUM> is at least about <NUM>, for example between about <NUM> and about <NUM>. In other embodiments, the mole ratio is between about <NUM> and about <NUM>. In some cases, the mole ratio is between about <NUM> and <NUM>. In other cases, the mole ratio is between about <NUM> and about <NUM>, for example between about <NUM> and about <NUM>. In some embodiments, the mole ratio is between about <NUM> and about <NUM>, for example, about <NUM>.

In some embodiments, the weight ratio of support material to catalyst complex is less than about <NUM>:<NUM>, for example, less than about <NUM>:<NUM>, or less than about <NUM>:<NUM>.

In at least one embodiment, the catalyst composition is <NUM> wt% (based on the total weight of the catalyst system) of a <NUM>:<NUM> BF<NUM>-MeOH complex on a SiO<NUM>/Al<NUM>O<NUM> support containing about <NUM> wt% Al<NUM>O<NUM>.

The catalyst composition can be <NUM> wt% (based on the total weight of the catalyst system) of a <NUM>:<NUM> BF<NUM>-MeOH complex on a Amberlyst or Amberlite support.

<FIG> is a flow diagram summarizing a method <NUM> of making a catalyst system according to one embodiment. Method <NUM> includes providing any metal oxide support material described herein at operation <NUM>. At <NUM>, the support material is calcined (or otherwise heated) at a predetermined temperature for a predetermined time as described above. Alternately, the support material is calcined (or otherwise heated) when first manufactured and/or recalcined (or reheated) as received. Method <NUM> includes forming the catalyst system by adding to the support material (a) a mixture comprising a Lewis acid (for example, BF<NUM>), (b) a mixture comprising a Lewis acid (for example, BF<NUM>) and a complexing agent, or (c) both at operation <NUM>. The complexing agent may be any complexing agent described herein, and may be used in excess. The catalyst system obtained is a solid.

<FIG> is a flow diagram summarizing a method <NUM> of making a catalyst system. Method <NUM> includes providing any ion exchange resin support material described herein at operation <NUM>. Method <NUM> also includes dehydrating (or otherwise heating) the support material at a predetermined temperature for a predetermined time at operation <NUM> as described above. Alternately, the support material is dehydrated (or otherwise heated) when first manufactured and/or re-dehydrated (or reheated) as received. Method <NUM> includes forming the catalyst system by adding to the support material (a) a mixture comprising a Lewis acid (for example, BF<NUM>), (b) a mixture comprising a Lewis acid (for example, BF<NUM>) and a complexing agent, or (c) both at operation <NUM>. The complexing agent may be any complexing agent described herein, and may be used in excess. The catalyst system obtained is a solid.

In some embodiments, addition of the mixture comprising a Lewis acid includes adding BF<NUM> gas uncomplexed with any complexing agent (as described herein). In such embodiments, the support material may be contacted with excess BF<NUM> gas in a stainless steel cylinder at a pressure of greater than about <NUM> psig (<NUM> kPa), for example, between about <NUM> psig (about <NUM> kPa) and about <NUM> psig (about <NUM> kPa), for about <NUM> hours. The cylinder is then vented and excess BF<NUM> is vented through a caustic scrubber.

Alternately, the catalyst complex (e.g., the Lewis acid and complexing agent) is added to the support material. In such cases, addition of the mixture comprising a Lewis acid and a complexing agent includes preforming the BF<NUM>/complexing agent (the catalyst complex).

In some cases, the support material is slurried in a solvent during contact with the catalyst complex. Examples of solvents include non-coordinating, non-oxygenate, nonreactive solvents including non-polar or weakly polar solvents, such as alkanes (for example, isopentane, hexane, n-heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and higher alkanes), although a variety of other materials including cycloalkanes, such as cyclohexane. Alternately, halogenated hydrocarbons can be used as a solvent, such as carbon tetrachloride (CCl<NUM>) and <NUM>,<NUM>-dichloroethane.

During addition of the catalyst complex to the support material, the temperature of the mixture of the catalyst complex and the support material is maintained between about <NUM> and about <NUM> (for example, between about <NUM> and about <NUM>, such as between about <NUM> and about <NUM>, or at about room temperature). The reaction mixture is stirred while maintaining the temperature. Contact time, which may be the same as, or may include, the stirring time, is typically greater than about <NUM> hours (for example, between about <NUM> hours and about <NUM> hours, such as between about <NUM> hours and about <NUM> hours, or between about <NUM> hours and about <NUM> hours).

The solid catalyst systems can be prepared by any means in which the support materials can be contacted with BF<NUM> gas and/or BF<NUM> catalyst complexes while maintaining the complexing temperature with the support materials as described above. The complexing reaction can be exothermic, and the reaction of the catalyst and/or catalyst complex with the support material should be controlled to avoid loss of BF<NUM>. Loss of BF<NUM> may occur by breaking of the BF<NUM> complex bonds with the substrate, liberating BF<NUM> gas which is then, at the higher temperatures, lost from the solid substrate. The catalyst and/or catalyst complex may be added by any mechanical means that allows sufficient mixing of the catalyst and/or catalyst complex with the support material. In at least one embodiment, the support material is placed in a rotating double cone mixer and the catalyst complex is added ratably such that the temperature is controlled within the desired range, e.g., not exceeding <NUM>-<NUM>.

In at least one embodiment, a tube-in-shell heat exchanger in which the support material is packed in the tubes and the cooling media is maintained on the jacket is used. In some embodiments, BF<NUM> gas and/or BF<NUM> catalyst complexes can be passed over the support material in the tubes until a maximum absorption, but less than excess, is obtained as evidenced by BF<NUM> or of the BF<NUM> catalyst complex exiting the tubes. If less than a maximum absorption is desired, the catalyst system can be back-blended with uncomplexed support material to the desired BF<NUM> concentration.

<FIG> is a flow diagram summarizing a method <NUM> of preparing a catalyst system according to another embodiment. In the method <NUM>, the catalyst system can be further modified by contacting the solid catalyst system with suitable modifying agents, for example, the oxygen containing and nitrogen containing complexing agents described above. Such embodiments allow for the catalytic properties of the catalyst system(s) to be adjusted, for example, with respect to formation of alpha-vinylidene olefin isomers. Method <NUM> includes providing any support material described herein (metal oxide or organic support, e.g., ion exchange resin) described herein at operation <NUM>. Method <NUM> includes calcining or dehydrating (or otherwise heating) the support material at a predetermined temperature for a predetermined time at operation <NUM> as described above. Alternately, the support material is dehydrated (or otherwise heated) when first manufactured and/or re-dehydrated (or reheated) as received. Operation <NUM> is dependent on the type of support material. Method <NUM> includes forming a first catalyst system by adding to the support material (a) a mixture comprising a Lewis acid (for example, BF<NUM>), (b) a mixture comprising a Lewis acid (for example, BF<NUM>) and a complexing agent, or (c) both at operation <NUM>. The complexing agent may be any complexing agent described herein. The first catalyst system obtained is a solid. Method <NUM> includes forming a second catalyst system by contacting the first catalyst system with one or more modifying agents at operation <NUM>.

In some embodiments, the modifying agents can be added to the catalyst during the catalyst manufacturing step. Alternately, the modifying agents can be added to the feed during the polymerization step to further fine tune the catalyst properties such as selectivity to form HR-PIB. Thus, there are various methods of preparing the catalyst system. In some embodiments, BF<NUM> gas is added to the support material. Alternately, BF<NUM>-complexing agent is added to the support material. In other embodiments, BF<NUM> gas is added to the support material and then complexing agent is added to the support material. In some embodiments, BF<NUM>-complexing agent is added to the support material, and then modifying agents can be added to the support material. In other embodiments, BF<NUM> gas is added to the support material, then complexing agent is added to the support material, and a modifying agent is additionally added to the isobutylene feed. In some embodiments, BF<NUM>-complexing agent is added to the support material, then modifying agents can be added to the support material, and a modifying agent is additionally added to isobutylene feed.

For example, the solid BF<NUM> complex is contacted with the modifying agent in a stirred or otherwise agitated vessel such as a rotating drum in which the modifying agent is sprayed onto the solid BF<NUM> complex and subsequently absorbed. The temperature should be maintained at less than about <NUM> by controlling the spray rate, or by cooling (for example with internal cooling coils or with an external jacket or both). The pressure should be greater than about <NUM> psig for example between about <NUM> and about <NUM> psig with pressure provided by a nitrogen pad. Once the prescribed amount of modifying agent has been added, the mixture is mixed for about an additional <NUM> hours after which time the mixing vessel is vented to atmospheric pressure and the thus formed catalyst discharged to storage containers. The containers are preferably padded with about <NUM> psig to about <NUM> psig of nitrogen. The amount of modifying agent is greater than about <NUM>:<NUM> mole ratio of modifying agent to BF<NUM> (such as a mole ratio between about <NUM>:<NUM> and about <NUM>:<NUM>, for example between about <NUM>:<NUM> and about <NUM>:<NUM>).

The polymerization processes described herein utilize one or more polymer precursors as input to the catalyst system, or to be contacted with a catalyst system to form one or more polymer compositions. The polymer compositions (described in more detail below) include polymers made from one or more polymer precursors. Polymer compositions may include homopolymers, copolymers, or both. Polymer precursors suitable for both the processes and polymer compositions described herein are described in greater detail in the following.

Processes according to particular embodiments produce polymer compositions (for example, polyisobutylene including alpha vinylidenes, beta vinylidenes, and internal vinylidenes). For instance, in certain process embodiments, polymer precursors are contacted with the catalyst system. Each of the polymer precursors used in processes (and/or included in polymer compositions) herein is from a feedstock, for example, a liquid feedstock.

In some embodiments, the feedstock comprises about <NUM> wt% isobutylene (for example, greater than about <NUM> wt%, such as greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, greater than about <NUM> wt%, or greater than about <NUM> wt%) based on a total weight of the feedstock. Alternately, the feedstock consists essentially of isobutylene.

In some embodiments, the feedstock comprises other butylenes and/or unreactive compounds including alkanes and isoalkanes, such as C<NUM> to C<NUM> alkanes and isoalkanes.

In some embodiments, the feedstock comprises isobutylene. Example feedstocks include raffinate-<NUM>, also known as raff-<NUM>, or C<NUM> raffinate. The actual composition of raffinate-<NUM> is variable depending on the source. A typical raffinate-<NUM> feedstock might contain about <NUM> wt% C<NUM>, about <NUM> wt% isobutane, about <NUM> wt% n-butane, about <NUM> wt% <NUM>-butene, about <NUM> wt% isobutylene, about <NUM> wt% cis- and trans-<NUM>-butene, and less than about <NUM> wt% butadiene, and less than about <NUM> wt% oxygenates. Other examples of raffinate-<NUM> feedstocks also include those provided in Table <NUM>.

The presence of oxygenates may affect the catalytic reaction. Some common oxygenates found in typical feedstocks; methanol, ethanol, dimethyl ether, diethyl ether, t-butanol, MTBE. While not wishing to be bound by theory, it is believed that oxygenates have a twofold impact on isobutylene polymerization: oxygenates can act as initiators for polymerization and thus can reduce molecular weight and broaden molecular weight distribution, and oxygenates can complex with the BF<NUM> catalyst possibly resulting in complexes that can yield undesirable PIB olefin isomers and the further complexing can reduce the activity of the catalyst.

The C<NUM> and the n-butane are unreactive and pass through the reactor unchanged and are removed from the reaction mixture in the downstream stripping steps. Reaction of isobutylene depends on various factors including reaction conditions, and thus adjusting conditions can allow for varied final products. The <NUM>- and <NUM>-butenes may react to varying degrees depending on the catalyst type and reactor conditions. The unreacted olefins may also be removed from the polymer product in the downstream stripping steps.

Another feedstock that can be used is the effluent from a dehydrogenation of isobutane to isobutylene. Typically, such effluents contain between about <NUM> wt% and about <NUM> wt% isobutylene, and between about <NUM> wt% and about <NUM> wt% isobutane, with the balance being C<NUM>, normal butanes, butylenes, and butadiene. This feedstock is particularly suitable when unreactive isobutane may be utilized, for example, in cooperation with an isobutane dehydrogenation unit.

In at least one embodiment, the feedstock comprises at least about <NUM> wt% isobutylene (for example, at least about <NUM> wt%, such as at least about <NUM> wt%) with the balance being isobutane and minor amounts of C<NUM>, normal butanes, butylenes, and butadiene. This feedstock is also suitable for production of HR-PIB.

When using any feedstock, any unreacted polymer precursor may be recycled.

Copolymers may be formed if other olefins (i.e. other polymerizable compounds) are present in the feedstock. Feedstocks comprising higher amounts of isobutylene as the olefin precursor more readily produce HR-PIB. However, feedstocks (such as raffinate streams, which have lower amounts of isobutylene) may be used. Raffinate streams contain, in addition to isobutylene, other butylenes including <NUM>-butene, and cis- and trans-<NUM>-butene. These butylene compounds can co-polymerize with the isobutylene to give butene segments in the polymer chain. These butylene compounds are less reactive than isobutylene and therefore tend to end cap growing of the polymer chains and produce lower Mn polymers. Also, the end-capped chains tend not to be alpha vinylidene groups. Reaction conditions can be adjusted to selectively polymerize isobutylene and minimize the normal butene reactions, usually involving lower temperatures reaction temperatures.

As noted previously, embodiments of the present invention include polymerization processes wherein polymer precursors are contacted with a catalyst system to form a polymer composition. The polymer compositions include polyisobutylene (PIB), and in particular highly reactive polyisobutylene (HR-PIB). For the polymerizations, BF<NUM> does not need to be mixed with a complexing agent, as BF<NUM> on the support material is capable of forming polymer compositions including PIB, and particularly HR-PIB. In other embodiments, the catalyst is complexed with a complexing agent and is capable of forming the same polymer compositions. Typically, use of a complexing agent helps produce PIB with a high content of alpha vinylidene olefin isomer. While not wishing to be bound by theory, it is believed that complexing BF<NUM> mediates some of the acidity of BF<NUM> and reduces the rate of isomerization of initially formed alpha vinylidene isomers to more internally located and less reactive isomers.

<FIG> is a flow diagram summarizing a method <NUM> of making a polymer composition according to one embodiment. The method includes providing a catalyst system at operation <NUM>. The catalyst system includes (a) any support material described herein (for example Group IIIA, Group IVA, and Group IVB metal oxides, and combinations thereof, such as Al<NUM>O<NUM>, ZrO<NUM>, TiO<NUM>, SnO<NUM>, CeO<NUM>, SiO<NUM>, SiO<NUM>/Al<NUM>O<NUM>, and combinations thereof); and (b) a Lewis acid (for example, BF<NUM>). In some versions, the catalyst system further comprises a complexing agent, including any complexing agent described herein.

Also disclosed is a catalyst system including (a) an organic support material (for example an ion exchange resin, such as an anionic exchange resin, a cationic exchanges resin (such as Amberlyst™ and Amberlite™ resins), and/or combinations thereof); and (b) a Lewis acid (for example, BF<NUM>). The catalyst system can further comprise a complexing agent, including any complexing agent described herein.

In some embodiments, a catalyst system includes (a) a combination of inorganic oxide (i.e., Al<NUM>O<NUM>, ZrO<NUM>, TiO<NUM>, SnO<NUM>, CeO<NUM>, SiO<NUM>, SiO<NUM>/Al<NUM>O<NUM>, and combinations thereof) and organic support (i.e., an ion exchange resin, such as an anionic exchange resin, a cationic exchange resin, or a combination thereof); and (b) a Lewis acid (for example, BF<NUM>). In some embodiments, the catalyst system further comprises a complexing agent, including any complexing agent described herein.

Method <NUM> further includes providing a feedstock comprising isobutylene at operation <NUM>. The feedstock can be a liquid feedstock. Any feedstock described herein may be used.

Method <NUM> includes forming a reaction mixture comprising the feedstock and the catalyst system at operation <NUM>, as described below. Method <NUM> further includes contacting the isobutylene with the catalyst system at operation <NUM> and obtaining a polymer composition at operation <NUM>. Polymer compositions are described below. In some embodiments, forming the reaction mixture comprising the feedstock and the catalyst system comprises flowing the catalyst system into a reactor and flowing the feedstock into the reactor, and wherein contacting the isobutylene with the catalyst system comprises maintaining a temperature of the reaction mixture at a predetermined temperature or range of temperatures.

It should be noted that one or more of the operations may occur before or after that shown in <FIG> or may occur simultaneously in some embodiments. For example, operation <NUM> may occur after operation <NUM>.

<FIG> is a flow diagram summarizing a method <NUM> of making a polymer composition according to another embodiment. The method <NUM> includes providing a catalyst system at operation <NUM>, and providing a feedstock comprising isobutylene at operation <NUM>. Operations <NUM> and <NUM> are described above according to operations <NUM> and <NUM>, respectively.

Method <NUM> further includes flowing the catalyst system into a reactor at operation <NUM> and flowing the feedstock comprising isobutylene into the reactor at operation <NUM> as described below. In some casess, the catalyst system is provided to the reactor as a slurry. The slurry may comprise the catalyst system and one or more oligomeric byproducts and/or light polymers from PIB polymerization itself (for example, C<NUM> to C<NUM> oligomers, such as C<NUM> and/or C<NUM> PIB, and PIB having a molecular weight between about <NUM> Da and about <NUM> Da). In some embodiments, the slurry optionally comprises a non-polar carrier solvent such as alkanes from octane through hexadecane and higher alkanes.

Method <NUM> includes forming a reaction mixture comprising the feedstock and the catalyst system at operation <NUM>, and includes maintaining a temperature of the reaction mixture at a predetermined temperature range, for example, between about -<NUM> and about <NUM>, at operation <NUM>.

Method <NUM> further includes contacting the isobutylene with the catalyst system at operation <NUM>, and obtaining a polymer composition at operation <NUM>. Polymer compositions are described below.

It should be noted that one or more of the operations may occur before or after that shown in <FIG> or may occur simultaneously in some embodiments. For example, operations <NUM> may occur after operation <NUM>.

Methods of making compositions can include an optional operation of calcining the support material as described above. In some embodiments, methods of making compositions include forming the catalyst system by adding to the support material (a) a mixture comprising BF<NUM>, (b) a mixture comprising BF<NUM> and a complexing agent, or (c) both.

In some embodiments, suitable concentrations of the catalyst system in the reaction mixture are greater than about <NUM> ppm based on a total weight of the catalyst feed, wherein a BF<NUM> concentration in the reaction mixture is about <NUM> ppm based on the total weight of the catalyst feed. In at least one embodiment, the concentration of the catalyst system in the reaction mixture is between about <NUM> ppm and about <NUM>,<NUM> ppm based on a total weight of the catalyst feed, and wherein a BF<NUM> concentration in the reaction mixture is between about <NUM> ppm and about <NUM>,<NUM> ppm based on the total weight of the catalyst feed. Alternately, the concentration of the catalyst system in the reaction mixture is between about <NUM>,<NUM> ppm and about <NUM>,<NUM> ppm based on a total weight of the catalyst feed, and wherein a BF<NUM> concentration in the reaction mixture is between about <NUM> ppm and about <NUM>,<NUM> ppm based on the total weight of the catalyst feed.

Furthermore, although known polymerization techniques may be employed, processes according to certain embodiments utilize particular conditions (e.g., temperature and pressure). Temperatures generally may include a temperature of between about -<NUM> to about <NUM>, for example, between about <NUM> and about <NUM> °C. Pressure may depend on the desired scale of the polymerization system. For example, in some polymerizations, pressure may generally be conducted at the autogenous pressure of the reaction mixture at the selected reaction temperature. In some embodiments, the pressure of the reactor is greater than about <NUM> psig (about <NUM> kPa) (for example, between about <NUM> psig (about <NUM> kPa) and about <NUM> psig (about <NUM> kPa), such as between about <NUM> psig (about <NUM> kPa) and about <NUM> psig (about <NUM> kPa), between about <NUM> psig (about <NUM> kPa) and about <NUM> psig (about <NUM> kPa), or between about <NUM> psig (about <NUM> kPa) and about <NUM> psig (and about <NUM> kPa)). Reaction pressure can depend on the type of reactor used. For continuous stirred tank reactors (CSTR) in which cooling is provided by ebullient cooling, that is by partial volatilization of the reaction mixture, the volatilization temperature, and thus the reaction temperature, is dependent on reactor pressure. Lower pressure provides lower temperatures, and for practical purposes, with the lower limit set by the boiling point of the reaction mixture at ambient pressure. In the case of butylenes, this is around about -<NUM> to about - <NUM>. In cases requiring lower temperatures, other inerts are added with lower boiling points, such as propane. In loop reactors or CSTR not using ebullient cooling reaction pressure is not an issue as long as the reaction mixture is maintained in the liquid phase. For PIB this is typically greater than about <NUM> psig (about <NUM> kPa), for example greater than about <NUM> psig (about <NUM> kPa).

In the polymerization processes described herein, the run time of the reaction is up to about <NUM> minutes (for example, up to about <NUM> minutes, such as between about <NUM> minute and about <NUM> minutes, between about <NUM> minute to about <NUM> minutes, or between about <NUM> to about <NUM> minutes).

Heterogeneous BF<NUM> catalyst system processes of the present disclosure are also characterized by reaction times of less than about <NUM> minutes (for example, less than about <NUM> minutes, less than about <NUM> minutes, or less than about <NUM> minute).

Times and temperatures are controlled such that no significant olefin isomerization occurs during polymerization and conversion and molecular weights are in desirable ranges. Reaction temperatures and pressures, and polymer precursor concentrations can be selected to control for the Mn of the polymer composition. For example, higher temperatures typically provide polymer compositions with higher Mn.

Temperature control in the reactor is obtained by offsetting the heat of polymerization with reactor cooling by using reactor jackets or cooling coils to cool the contents of the reactor, auto refrigeration, pre-chilled feeds, vaporization of liquid medium (diluent, polymer precursors, or solvent) or combinations of all three. In the case of CSTR with ebullient cooling, the boiling mixture is cooled with a chilled overhead condenser. For non-ebullient cooled CSTR any type of heat exchanger could be used to chill the reactor jacket using any suitable cooling media. In some embodiments, a fast reactor is used. A fast reactor is one in which the reactor is the heat exchanger with the reaction taking place in the tubes with cooling on the shell. Any type of suitable cooling media can be used depending mainly on operating temperature range. Adiabatic reactors with pre-chilled feeds may also be used. In some embodiments, the reactor(s) is operated in as much of an isothermal mode as possible. Non-isothermal reactor operation results in broader molecular weight distributions. In series operation, the second reactor temperature is higher than the first reactor temperature. In parallel reactor operation, the temperatures of the two reactors are independent.

Suitable reactors for the polymerization include batch, continuous stirred tank reactor (CSTR), plug flow, fluidized bed, immobilized bed, and fixed bed. More than one reactor may be operated in series or parallel. These reactors may have or may not have internal cooling or heating, and the feeds may or may not be refrigerated.

In some embodiments, and for CSTR, the catalyst system is slurried with one or more oligomeric byproducts and/or light polymers from PIB polymerization itself (for example, C<NUM> to C<NUM> oligomers, such as C<NUM> and/or C<NUM> PIB, and PIB having a molecular weight between about <NUM> Da and about <NUM> Da), at about a <NUM> wt% concentration. The catalyst system slurry is then injected into the incoming feed stream. In some embodiments, the catalyst system slurry is injected into the incoming feed stream at a point where the physical distance between the injection point in the feed line and the point at which the feed enters the reactor is at a minimum. In some embodiments, the injection point for the catalyst may be on the suction side of the feed pump to provide mixing. In some embodiments, the slurry optionally comprises a non-polar carrier solvent such as alkanes from octane through hexadecane and higher alkanes. In some embodiments, the concentration of the catalyst system in the reaction mixture for CSTR is between about <NUM>,<NUM> ppm and about <NUM>,<NUM> ppm based on a total weight of the catalyst feed, wherein a BF<NUM> concentration is between about <NUM> ppm and about <NUM> ppm based on the total weight of the feed. Residence times are on the order of less than about <NUM> minutes (for example, about <NUM> minutes, such as less than about <NUM> minutes, or between about <NUM> minutes to about <NUM> minutes) and can be controlled by catalyst system concentration. Higher catalyst system concentrations, up to a point, increase the reaction rate. The polymerization reaction is highly exothermic and a limiting factor to reaction rate is the ability to remove the heat of reaction.

In conventional plants that utilize CSTR, the reaction mixture comprising the catalyst system is flowing upward in the reactor, through at least a first portion and a second portion. The first portion of the reactor is relatively narrow to provide higher velocity and higher catalyst system mixing. The second portion of the reactor is wider to provide lower velocity and less catalyst system mixing, allowing for some settling of the catalyst system back into the reaction zone. The crude reaction mixture exits near the top of the reactor with some catalyst system being carried out with the exiting crude reaction mixture. The catalyst system exiting the reactor is made up with the catalyst system injection such that a constant catalyst system amount is maintained in the reactor. The reaction temperature can be maintained by vaporization of a portion of the isobutylene containing feed controlled by the reactor pressure; higher reactor pressure gives higher reaction temperature according to the vapor pressure curve of the system butylenes. Mn of the polymer is controlled by reaction temperature with higher reaction temperature giving lower Mn. Reaction temperatures between about -<NUM> and about <NUM> provide polymers having an Mn of about <NUM>,<NUM> daltons. Reaction temperatures between about <NUM> and about <NUM> provide polymers having an Mn of about <NUM>,<NUM> daltons. The crude reaction mixture leaving the reactor is treated with aqueous caustic streams to quench and wash out the catalyst system.

Alternately, these plants can be modified to include a catalyst system filtration (or other solid-liquid separation devices as described below) to remove the catalyst system thereby eliminating the water washing operations and the need to dispose of waste water containing catalyst system residues. Optionally, a water washing operation may be performed depending on application or type of plant. Removal of the catalyst system also allows for recycling of the catalyst system. The plants can also include one or more distillation columns as described below. Any standard Cosden type polymerization units (such as CSTR plants using ebullient cooling) can employ the technology described in this disclosure. Other plants can be used such CSTR plants without ebullient cooling and tubular reactor plants.

In some embodiments, and for fast reactor modes, the reactor is a tube-in-shell heat exchanger with the reaction taking place in the tubes and cooling provided through the shell side of the heat exchanger with the heat of reaction taken out by an external chiller unit.

One reactor design is a two-pass heat exchanger. Using a slurried catalyst system, the reaction is carried out in the liquid phase at pressures of at least about autogenous pressures, typically greater than about <NUM> psig (<NUM> kPa) (for example, between about <NUM> psig (about <NUM> kPa) and about <NUM> psig (about <NUM> kPa), between about <NUM> psig (about <NUM> kPa) and about <NUM> psig (about <NUM> kPa), or between about <NUM> psig (about <NUM> kPa) and about <NUM> psig (about <NUM> kPa)).

In some embodiments, a tubular loop reactor is used. In such embodiments, the circulation loop is provided to deliver high velocity in the tubes at a Reynold's number of the circulating liquid in the tubes greater than about <NUM>,<NUM>. In some embodiments the residence time in the reactor is less than about <NUM> minutes (for example, less than about <NUM> minutes, less than about <NUM> minutes, less than about <NUM> minutes, less than about <NUM> minutes, less than about <NUM> minutes, less than about <NUM> minutes, less than about <NUM> minutes, or less than about <NUM> minute; alternately, between about <NUM> seconds and about <NUM> minutes). Reynolds numbers greater than about <NUM>,<NUM> allow for turbulent flow in the tubes which increases the heat exchange and the ability to remove the heat of reaction in very short periods of time. The ability to quickly remove the heat of reaction allows for operation at very short residence times. The concentration of the catalyst system in the reaction mixture is between about <NUM> ppm and about <NUM>,<NUM> ppm based on a total weight of the catalyst feed, and wherein a BF<NUM> concentration in the reaction mixture is between about <NUM> ppm and about <NUM>,<NUM> ppm based on the total weight of the catalyst feed. In some embodiments, the concentration of the catalyst system in the reaction mixture is between about <NUM>,<NUM> ppm and about <NUM>,<NUM> ppm based on a total weight of the catalyst feed, and wherein the BF<NUM> concentration in the reaction mixture is between about <NUM> ppm and about <NUM>,<NUM> ppm based on the total weight of the catalyst feed. Alternately, the concentration of the catalyst system in the reaction mixture is greater than about <NUM>,<NUM> ppm based on a total weight of the catalyst feed, and wherein the BF<NUM> concentration is greater than about <NUM> ppm based on the total weight of the catalyst feed.

In some embodiments, the reactor system is a tubular loop reactor in which the Reynold's number of the circulating liquid in the tubes is greater than about <NUM>,<NUM> and the residence time in the reactor is less than about <NUM> minutes (for example, less than about <NUM> minutes, less than about <NUM> minutes, less than about <NUM> minutes, less than about <NUM> minutes, less than about <NUM> minutes, less than about <NUM> minutes, less than about <NUM> minutes, or less than about <NUM> minute; alternately, between about <NUM> seconds and about <NUM> minutes) such that the solid catalyst system is immobilized in the tubes by attaching the catalyst system particles to a suitable substrate. Because the catalyst system is constrained in the tubes, no post reaction recovery is required. Suitable substrate compositions and geometries for attaching the solid BF<NUM> catalyst system particles can include ceramic mats such as those sold by NGK Insulators for use in modern catalytic convertors, or wire mesh or wire fibers. As such, the catalyst system particles (or catalyst complex) can be used in fixed bed reactors to produce HR-PIB. The solid catalyst systems of the present disclosure can be further attached or otherwise immobilized to other solid substrates chemically, physically, or mechanically means, or a combination thereof.

For tubular loop reactors, the catalyst system is slurried with one or more oligomeric byproducts and/or light polymers from PIB polymerization itself (for example, C<NUM> to C<NUM> oligomers, such as C<NUM> and/or C<NUM> PIB, and PIB having a molecular weight between about <NUM> Da and about <NUM> Da), at about <NUM> wt% catalyst system concentration. The catalyst system slurry is then injected into the incoming feed stream. In some embodiments, the catalyst system slurry is injected into the incoming feed stream at a point where the physical distance between the injection point in the feed line and the point at which the feed enters the reactor is at a minimum. In some embodiments, the injection point for the catalyst may be on the suction side of the feed pump to provide mixing. In some embodiments, the slurry optionally comprises a non-polar carrier solvent such as alkanes from octane through hexadecane and higher alkanes.

After the reaction effluent leaves (or is discharged from) the CSTR, tubular loop, or other reactors, the reaction effluent may be purified by separation, atmospheric stripping, vacuum stripping, or a combination thereof to remove byproducts, unreactive compounds, catalyst residues, and unreacted polymer precursors. Unreacted polymer precursors may be recycled. For example, such purification may be accomplished in a plant by passing the crude polymer composition through a solid-liquid separation device and then through a pressure distillation column to remove the unreacted polymer precursors and other non-reacted residues. The distillation columns may be atmospheric and/or vacuum distillation columns.

Passing the crude polymer compositions through a solid-liquid separation device serves to separate solid catalyst system particles, unreacted residues, and other solids from the crude polymer compositions. Distilling serves to separate dimers, oligomers, unreacted polymer precursors, unreactive compounds, and other non-reacted residues from the polyisobutylene polymer composition.

Accordingly, and in some embodiments, the method of making a polymer composition includes discharging the polymer composition from the reactor; feeding the polymer composition one or more suitable separation apparatuses (for example one or more of a suitable solid-liquid separation devices (such as filters, centrifugation devices, and cyclone separation devices), and one or more of a distillation devices (e.g., distillation columns)); and discharging the polymer composition from the one or more separation apparatuses. Any of those operations may be repeated one or more times.

In the distilling operation, the crude polyisobutylene polymer is treated in a distillation column to remove unwanted species. The distilling operation can include passing the crude polyisobutylene polymer composition to a first distillation column, feeding the crude polyisobutylene polymer composition under pressure in the first distillation column so as to remove unreacted polymer precursors (e.g., isobutylene) and unreactive compounds (e.g., isobutane and isobutylene) from the crude polyisobutylene polymer composition, and discharging the polyisobutylene polymer composition from the first distillation column. The distilling operation may further include passing the discharged polyisobutylene polymer composition from the first distillation column to a second distillation column, feeding the polyisobutylene polymer composition in the second distillation column at atmospheric pressure so as to remove C<NUM> (dimer) byproducts from the polyisobutylene polymer composition, and discharging the polyisobutylene polymer composition from the second distillation column. The distilling operation may further include passing the discharged polyisobutylene polymer composition from the second distillation column to a third distillation column, feeding the polyisobutylene polymer composition in the third distillation column under vacuum conditions so as to remove higher oligomer byproducts (e.g., C<NUM> and C<NUM>) from the polyisobutylene polymer composition, and discharging the polyisobutylene polymer composition from the third distillation column. Any of those operations may be repeated one or more times.

Each of the various polymerization processes described herein can be carried out using general polymerization techniques known in the art. Any suspension, homogeneous, bulk, slurry, solution slurry, or gas phase polymerization process known in the art can be used. Such processes can be run in a batch, semi-batch, or continuous mode. In some embodiments, homogeneous polymerization processes and slurry processes are used. A homogeneous polymerization process is defined to be a process where at least about <NUM> wt% of the product is soluble in the reaction media. A bulk process is defined to be a process where polymer precursors itself are used as the reaction medium and the concentration of polymer precursors in all feeds to the reactor is about <NUM> vol% or more. Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the polymer precursors). In another embodiment, the process is a slurry process. In the slurry process, a suspension of supported catalyst is employed and polymer precursors are polymerized on the catalyst particles and/or catalyst systems.

In some slurry process embodiments, the suspension includes diluent. The suspension can be intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.

In some embodiments, the polymerization is conducted in an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof, and the like). Other additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, reducing agents, and oxidizing agents.

The polymerization processes described herein produce polymer compositions. In some embodiments, the polymer compositions are polyisobutylenes having one or more of the following properties:.

In addition to isobutylene olefin isomers, by-products of the polymerization can include C<NUM>-C<NUM> by-products, for example, dimers (C<NUM>) and oligomers (C<NUM>-C<NUM>). Copolymers may also be produced if other olefin precursors are present in the feedstock. Feedstocks comprising higher amounts of isobutylene as the polymer precursor more readily produce HR-PIB. However, feedstocks (such as raffinate streams, which have lower amounts of isobutylene) may be used. Raffinate streams contain, in addition to isobutylene, other butylenes including <NUM>-butene, and cis- and trans-<NUM>-butene. These butylene compounds can co-polymerize with the isobutylene to give butene segments in the polymer chain. These butylene compounds are less reactive than isobutylene and therefore tend to end cap growing of the polymer chains and produce lower Mn polymers. In addition, the end-capped chains tend not to be alpha vinylidene groups. Reaction conditions can be adjusted to selectively polymerize isobutylene and minimize the normal butene reactions, usually involving lower temperatures reaction temperatures.

Any of the foregoing polymers, including compounds thereof, may be used in a variety of end-use applications, including any application suitable for PB, PIB, and HR-PIB. Examples of applications for HR-PIB include subsequent derivatization reactions to produce fuel and lubricant additives. Examples of applications for PIB and HR-PIB include adhesives, sealants, lubricants & greases, metal working, cosmetics, and mining.

Polymer Compositions. The type and amount of each olefin isomer (i.e., alpha vinylidene, beta vinylidene, and other isomers) is determined by <NUM>C NMR.

<NUM>C NMR spectra were collected using a <NUM> Bruker pulsed fourier transform NMR spectrometer equipped with a <NUM> Broad Band Observation (BBO) probe at about room temperature. The polymer sample is dissolved in chloroform-d (CDCl<NUM>) and transferred into a <NUM> glass NMR tube. Typical acquisition parameters are inverse-gated (IG) decoupling, a <NUM>° pulse, and a <NUM> second relaxation delay. Chemical shifts are determined relative to the CDCl<NUM> signal which is set to about <NUM> ppm. To achieve maximum signal-to-noise for quantitative analysis, multiple data files may be added together. The spectral width was adjusted to include all of the NMR resonances of interest. <NUM>C NMR shifts for the olefin carbon atoms are provided below in Table <NUM>.

Polymer molecular weight: Molecular weights (weight-average molecular weight, Mw, number-average Molecular weight, Mn) and PDI (ratio of Mw/Mn) are determined using gel permeation chromatography (GPC). Equipment includes a Waters Alliance <NUM> HPLC system with a differential refractive index detector (DRI). A typical GPC procedure is to dissolve the sample to be tested in tetrahydrofuran (THF) at a concentration of about <NUM> wt% to about <NUM> wt%. The polymer solution is pumped through a series of columns packed with Styragel™ beads of known porosity. Typical pore diameters range from about <NUM>,<NUM>Å down to about <NUM>-<NUM>Å, and a typical column string includes a <NUM><NUM> Å column, a <NUM><NUM> Å column, a <NUM>Å column and an about <NUM>-<NUM>Å columns. For example, Waters Styragel™ HR columns <NUM>, <NUM>, and <NUM> can be used. The nominal flow rate is about <NUM>/min. The various transfer lines, columns and differential refractometer (the DRI detector) are contained in an oven maintained at about <NUM>. Elution solvent is THF. There is a <NUM>-sample carousel for automatic injections. Empower <NUM> is the software system for controlling the separation and analysis.

The columns are calibrated with known molecular weight standards, both narrow distribution standards and broad distribution standards (for example, polystyrene standards from a molecular weight of <NUM> to <NUM>). From the calibration, Mn and Mw can be determined for a polymer sample. PDI is the ratio of Mw/Mn.

Polymer solutions for GPC are prepared by placing the dry polymer in a glass container, adding the desired amount of THF, and then filtering the mixture through a <NUM>-micron nylon or PTFE filter. All quantities are measured gravimetrically. The concentration of polymer to THF is about <NUM> to <NUM>/ml
Prior to running each sample the DRI detector and the injector are purged. Flow rate in the apparatus is then increased to about <NUM>/minute, and the DRI is allowed to stabilize for about <NUM> hours to about <NUM> hours before injecting the first sample. Each sample run takes about one hour to complete.

The present disclosure, while not meant to be limited by, may be better understood by reference to the following examples and tables.

Catalyst System Examples <NUM>-<NUM>: Calcination of support material and addition of Lewis acid to gamma-alumina support material. Gamma-alumina beads (CSS <NUM>γ-alumina spheres purchased from BASF Corporation) were calcined for about <NUM> hours at various temperatures (i.e., about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, and about <NUM>). The beads were treated with an excess of BF<NUM> gas in a stainless-steel cylinder at a pressure of about <NUM> psig (about <NUM> kPa) for about <NUM> hours to form catalyst system examples <NUM>-<NUM>. The cylinder was then vented and any remaining excess BF<NUM> was vented through a caustic scrubber. The active amount of BF<NUM> gas absorbed by the support material was determined gravimetrically.

The data are summarized in Table <NUM> and show that the concentration of BF<NUM> on the alumina at calcination temperatures below about <NUM> is about <NUM> wt% BF<NUM>. As the calcination temperature is increased above about <NUM>, the concentration of BF<NUM> on the alumina increased to between about <NUM> wt% and about <NUM> wt% and remained about constant up to about <NUM>. Calcination temperatures for these gamma alumina beads are, for example, between about <NUM> and about <NUM>, such as, between about <NUM> to about <NUM>. Gamma-alumina support material calcination temperatures above about <NUM> can result in sintering of the gamma-alumina support material resulting in decreased surface area.

Polymer Composition Example <NUM>: Polymerization of isobutylene to make HR-PIB using the BF<NUM> on gamma-alumina catalyst system. A total weight of about <NUM> of high purity isobutylene (HPIB) containing greater than <NUM> wt% isobutylene was charged to a <NUM> pressure bottle and cooled using an ice/salt bath to a temperature of about -<NUM>. About <NUM> grams, <NUM>,<NUM> ppm, of BF<NUM> on alumina beads (at about <NUM> wt% active BF<NUM>) was added to the isobutylene reaction mixture with stirring. Stirring was maintained during the course of the reaction. After about <NUM> minutes, the reaction was quenched by decanting the mixture while still cold to remove the catalyst beads. Optionally, the crude mixtures may be washed with water. The reaction mixture was then heated at about <NUM> for about <NUM> hours to remove unreacted isobutylene. Gravimetric analysis showed conversion to HR-PIB was about <NUM>%. This crude, unstripped sample was analyzed by <NUM>C NMR and found to contain about <NUM> wt% alpha vinylidene olefin isomer with a molecular weight (Mn) of about <NUM> daltons. Conversion is the amount of HPIB converted to dimers, oligomers and HR-PIB, and selectivity is the amount of converted isobutylene that is HR-PIB product, excluding dimers and oligomers.

The crude, unstripped sample (about <NUM>) was then charged to a <NUM> boiling flask and stripped using a distillation column at a temperature setting of about <NUM> for about <NUM> hour, then at a setting of about <NUM> for about <NUM> hour and then at a setting of about <NUM> for about <NUM> hour. The maximum internal temperature reached was about <NUM>. The final stripped sample was analyzed by <NUM>C NMR and found to contain about <NUM> wt% alpha vinylidene olefin isomer with a Mn of about <NUM> daltons. Gravimetric analysis of the final stripped sample indicated the selectivity to HR-PIB to be <NUM> wt%.

Stripping removed some light oligomers that had olefin isomer compositions other than contained in the actual HR-PIB polymer. Removal of the oligomer products of low Mn further had the effect of increasing the average product Mn. An Mn increase on stripping is due to removal of low Mn by-products. The concomitant increase in alpha vinylidene amount is also due to removal of by-products which, themselves are not particularly high in alpha vinylidene.

Catalyst System Examples <NUM>-<NUM>: Calcination of support material and addition of Lewis acid/complexing agent to the silica-alumina support material. Silica-alumina support materials (ALS <NUM> and ALS <NUM>) containing various ratios of SiO<NUM>/Al<NUM>O<NUM> were calcined at about <NUM> for a time greater than about <NUM> hours. Catalyst complex (BF<NUM>-MeOH (<NUM>:<NUM>)) was added to the support materials to form catalyst system examples <NUM> and <NUM>. BF<NUM>-MeOH catalyst complexes are passed over the support material until a maximum absorption, but less than excess, is obtained as evidenced by the BF<NUM>-MeOH catalyst complex exiting the tubes.

During addition of the catalyst complex to the support material, the mixture of the catalyst complex and the support material was maintained at temperatures between about <NUM> and about <NUM> with heating or cooling as required. The reaction time was about <NUM> hours. A tube-in-shell heat exchanger was used for the reaction with the complexing reaction taking place in the tubes and heating or cooling as required on the shell side.

Table <NUM> shows the BF<NUM>-MeOH capacity of two silica-alumina support materials having two different ratios of SiO<NUM>/Al<NUM>O<NUM> with different porosities. The ALS <NUM> had the higher porosity and had the higher capacity for BF<NUM>-MeOH complex. While not wishing to be bound by theory, it is believed that this result indicates that at least some of the BF<NUM> complex is absorbed in the pores of the substrate due to the higher pore volume of ALS <NUM>.

Polymer Composition Example <NUM>: Polymerization of isobutylene to make HR-PIB using catalyst system example <NUM> (BF<NUM>-MeOH (<NUM>:<NUM>) catalyst complex on ALS <NUM> support material). A total weight of about <NUM> of high purity isobutylene (HPIB) containing greater than about <NUM> wt% isobutylene was charged to a <NUM> pressure bottle and cooled using an ice/salt bath to a temperature of about -<NUM>. Catalyst system example <NUM> (about <NUM>) was added to the isobutylene reaction mixture with stirring. After about <NUM> minutes, the reaction mixture was filtered to remove the catalyst system and then heated at about <NUM> for about <NUM> hours to remove unreacted isobutylene. Optionally, the crude reaction mixture may be washed with water. Gravimetric analysis showed conversion (amount of isobutylene that reacted) of about <NUM>%, the balance being Cs, C<NUM> and C<NUM> olefin oligomers and by-products. These oligomers and byproducts are removed in one or more stripping steps. Stripping removed some light oligomers that had olefin isomer compositions other than contained in the actual HR-PIB polymer. Removal of the oligomer products of low Mn further had the effect of increasing the average product Mn.

The devolatilized reaction mixture was then heated at a temperature setting of about <NUM> for about <NUM> hour, and then at a setting of about <NUM> for about <NUM> hour. The maximum internal temperature reached was about <NUM>. Gravimetric analysis showed conversion (amount of isobutylene that reacted) of about <NUM>%. GPC analysis showed the resulting PIB product had a Mn of about <NUM> daltons. <NUM>C NMR showed the alpha vinylidene content to be about <NUM>%.

By adjusting the catalyst composition, by for example increasing the ratio of complexing agent to BF<NUM>, and/or slowing the polymerization reaction, the amount of alpha vinylidene content can be increased.

The examples show that solid catalyst systems for producing HR-PIB can be made by calcining support material comprising metal oxides at various temperatures and subsequently adding to the support material a mixture comprising a catalyst (e.g., BF<NUM> gas), a mixture comprising a catalyst complex (e.g., BF<NUM>/complexing agent), or combinations thereof. These solid catalyst systems are dispersed in a reaction mixture to effect the polymerization of feedstocks comprising isobutylene to polyisobutylene compositions having desired olefin isomer content, in which the alpha vinylidene isomer content is greater than about <NUM> wt%.

The solid catalyst systems described herein show benefits over conventional liquid catalyst systems. Because the catalyst systems are solids, the catalyst systems can be removed by simple filtration, thus eliminating the need for extensive water washing and generating large amounts of waste water containing BF<NUM> salts seen with liquid catalyst systems. Catalyst washing is very cumbersome, tedious, and generates large amounts of waste water that needs disposal, usually off-site. Disposal of this waste water can be expensive and limits the plant site options. Also, the washed catalyst cannot be recovered or recycled. Moreover, because the solid catalyst systems are dispersible, a fixed bed is not required.

Solid catalyst systems comprising BF<NUM> of the present disclosure can eliminate the problem of handling toxic BF<NUM> gas at an HR-PIB production site. These solid catalyst systems can act like BF<NUM> gas in that they can be complexed further on-site, as described in by method <NUM>, with suitable complexing agents to optimize the HR character of the PIB product, but without the hazards and dangers of handling BF<NUM> gas on site.

Claim 1:
A catalyst system, comprising:
a support material selected from the group consisting of Al<NUM>O<NUM>, ZrO<NUM>, TiO<NUM>, SnO<NUM>, CeO<NUM>, SiO<NUM>, SiO<NUM>/Al<NUM>O<NUM>, and combinations thereof, the support material having an Al<NUM>O<NUM> content between <NUM> wt% and <NUM> wt% based on the total weight of the support material; and
BF<NUM>, wherein the concentration of BF<NUM> is greater than <NUM> wt% based on the total weight of the catalyst system.