CA2109845A1 - Immobilized lewis acid catalysts - Google Patents

Abstract

Immobilized Lewis Acid catalyst comprising polymer having at least one Lewis Acid immobilized within the structure therein, said polymer having monomer units represented by the structural formula: --[A]a--[B]b--[C]c-- wherein a represents about 1 to about 99 mole %; b represents about 0 to about 50 mole %; c represents about 1 to about 99 mole %; a + b + c is preferably about 100 %; A is (.alpha.); B is (.beta.); C is selected from the group consisting of (I), (II), and (III) combinations thereof, wherein D is OH, halide, OR4, NH2, NHR3, OM', or OM''; E is the residue of the reaction of at least one Lewis Acid with the D substituent of monomer unit B; R1 represents proton, C1-C24 alkyl group, or C3-C24 cycloalkyl; R2 represents C1-C24 alkylene group, C3-C24 cycloalkylene, C6-C18 arylene, or C7-C30 alkylarylene; R3 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl; R4 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl; M' represents alkali metal; M'' represents alkaline-earth metal. Also disclosed are polymerization and alkylation processes utilizing the immobilized Lewis Acid catalysts.
Another aspect of the present invention is a method of manufacturing immobilized Lewis Acid catalysts.

Description

W093/00373 PCT/US92/054~
~10$8~

MNOB~IZED LE~I8 ACID CATA~Y8T~

CROSS-~EFERENCE To RELATED APPLICATIONS
This application is a Continuation-In-Part of U.S. Serial No. 723,130 filed on June 28, i991, which is hereby incorporated by reference.

TECHNICA~ D
The field of art to which this invention pertains is catalysts, in particular, immobilized Lewis Acid catalysts, and a process to prepare polymer using said catalysts as well as the polymer product.

8ACKGROUND OF ~IE INVE13TION
Lewis Acids have been widely used as catalysts in carbocationic pclymerization processes to catalyze the polymerization of monoolefins. Examples of Lewis Acid catalysts include AlCl3, BF3, BCl3, TiC14~ Al(C2H5)3, Al(C2Hs)2Cl, and Al(C2H5)Cl2. Such carbocationic polymerization catalysts have many advantages, including high yield, fast reaction rates, good molecular weight control, and utility with a wide variety of monomers. However, conventional carbocationic polymerization processes typically employ Lewis Acid catalysts in unsupported form. Hence, these catalysts, typically, cannot be recycled or reused in a cost effective manner.
In a typical carbocationic polymerization process, such as the car~ocationic polymerization of isobutylene, a catalyst feedstream in a li~uid or gaseous form and a monomer feedstream a;:e fed simultaneously into a conventional reactor. In the reactor, the streams are interminqled and contacted under process conditions such that a desired fraction of the monomer feedstream is polymerized. Then, after an appropriate residence time in the reactor, a SUBSTITUTE SHEET

W093/00373 PCT/US92/0~ ~

21~3h~5 discharge stream is withdrawn from the reactor. The discharge stream contains polymer, unreacted monomer and catalyst. In order to recover the polymer, the catalyst ~nd unreacted monomer must be separated from this stream. Typically, there is at least some residue of catalyst in the polymer which cannot be separated.
After separation, the catalyst is typically quenched and neutralized. The quenching and neutralization steps tend to generate large quantities of waste which must typically be disposed of as hazardous waste.
The recycling or reuse of Lewis Acid catalysts used in polymer processes is difficult because o~ the chemical and physical characteristics of these catalysts. For example, most Lewis Acid catalysts are no~-volatile and cannot be distilled off.
Other catalysts are in a solid particulate form and must be separated from the polymer stream by physical separation means. Some Lewis Acid catalysts are gaseous, such as BF3. The gases can be recycled and reused, but with considerable difficulty, by utilizing gas-liquid separators and compressors.
There have been several attempts made to support Lewis Acid catalysts on the surface of inorganic substrates such as silica gel, alumina, and clay. Although these approaches are somewhat successful in recycling the Lewis Acid catalysts, there are everal disadvantages associated with their use.
one particularly strong disadvantage is that these approaches to supported catalysts generally produce only low molecular weight oligomers. Another disadvantage is that the catalysts (supported on inorganic substrates) typically leach out during the reaction since the catalysts tend to not be firmly fîxed to the supporting substrates.
Attempts to support Lewis Acid catalysts can be characterized as ~alling into two basic classes;

SUBSrITUTE SHEET

WOg3/00373 PCT/US92/0~4~

2 ~ 0 3 ~ !

namely, those which rely on physical adsorption and those wherein the Lewis Acid chemically reacts with the support.
U.S. Patent No. 3,925,49S discloses a catalyst consisting of graphite having a Lewis Acid intercalated in the lattice thereof.
U.S. Patent No. 4,112,011 discloses a catalyst comprising gallium compounds on a suitable support such as aluminas, silicas and silica aluminas. ' U.S. Patent No. 4,235,756 discloses a catalyst comprising porous gamma alumina impregnated with an aluminum hydride.
U.S. Patent No. 4,288,449 discloses chloride alumina catalysts.
U.S. Patent Nos. 4,734,472 and 4,751,276 disclose a method for preparing functionalized (e.g., hydroxy functionalized) alpha-olefin polymers and copolymers derived from a boran~ containing intermediate.
- U.S. ~Patent No. 4,167,616 discloses polymerization with diborane adducts or oligomers of boron-containing monomers.
U.S. Patent No. 4,698,403 discloses a process for the ~preparation of ethylene copolymers`~ in the presence of selected nickel-containing catalysts.
U.S. Patent No. 4,638,092 discloses organo-boron compounds with strong aerobic initiator action to start polymerizations.
~ U.S. Patent No. 4,342,849 discloses novel telechelic polymers formed by hydroborating diolefins to polyboranes and oxidizing the polymeric boranes to form the telechélic dehydroxy polymer. No use of the resulting polymer to support Lewis Acid catalysts is disclosed.
~ U.S. Patent No. 4,558,170 discloses a continuous cationic polymerization process wherein a SUBSrlTUTE SHEET

WOg3/~373 PCT~US92/0~ ~
, 2 1 ~ 9 8 ~

cocatalyst is mixed with a monomer feedstream prior to introduction of the feedstream to a reactor containing a Lewis Acid catalyst.
U.S. Patent Nos. 4,719,190, 4,798,190 and 4,g29,800 disclose hydrocarbon conversion and polymerization catalysts prepared by reacting a solid adsorbent containing surface hydroxyl groups with certain Lewis Acid catalysts in halogenated solvent.
The only disclosed adsorbents are inorganic; namely,' silica alumina, boron oxide, zeolite, magnesia and titania.
U.S. Patent No. 4,605,808 discloses a process for producing polyisobutene using a complex of boron trifluoride and alcohol as catalyst.
U.S. Patent No. 4,139,417, discloses amorphous copolymers of monool~fins or of monoolefins and nonconjugated dienes with unsaturated derivatives of imides. In the preparation of the polymer the imide is complexed with a Lewis Acid catalyst.
Japanese Patent Application No. 188996/1952 (Laid Open No. J59080413A/1984) discloses a process for preparing a copolymer of an olefin and a polar vinyl monomer which comprises copolymerizing an olefin with a r. complex of the polar vinyl-monomer and a Lewis acid.
European Patent Application No. 87311534.9 (Publication No. EPA 0274912) discloses polyalcohol copolymers-made using borane chemistry.
T. C. Chung and D. Rhubright, Macromolecules.
Vol. 24, 970-972, (lg91) discloses functionalized polypropylene copolymers made using borane chemistry.
~ T. C. Chung, Journal of Inor~anic and Orqanometallic PolYmers, Vol. 1, No. 1, 37-51, (1991) discloses the preparation of polyboranes and borane monomers.
U- S- Patent No- 4,849,572 discloses a process for~preparing polybutenes having enhanced reactivity SUBSTITUTE SHEET

W093/00373 PCT/US9~
21~8~S

using a BF3 catalyst. Polybutene is produced which has a number average molecular weight in the range of from 500 to 5,000. The polymer has a total terminal double-bond content of at least 40~ based on total theoretical unsaturation of the polybutene~ The polybutene contains at least so% by weight iso~utylene units based on the polybutene number average molecular weight. The process is accompliched by contacting a feed supply comprising at least 10% by weight isobutylene based on' the weight of the feed with a BF3 catalyst under conditions to cationically polymerize the feed in liquid phase to form polybutene. The polymer is immediately quenched with a quench medium sufficient to deactivate the BF3 catalyst.
There has been a continuous sear~h for catalysts having high efficiency which can be recycled or reused in cationic polymerization processes. The present invention was developed pursuant to this search.

SUMMARY OF,THE ~V NTION
one aspect of the present invention provides immobilized Lewis Acid catalyst, comprising polymer having at least one Lewis Acid immobilized within the structure therein, said polymer having repeating monomer units represented by the structural formula:

----[A]a~--~B]b---[C]c~~

wherein a represents about 1 o about 99 mole %, b represents ~out 0 to about 50 mole %, c represents about 1 to about 99 mole ~, a + b + c is preferably about 100%;

SUBSTITUTE SHEET

WOg3/00373 PCT/US92/0S4~4 .,", ~ .

2 1Q`&~ 6 -Rl 1 A is t CH2 - C~

B is t CH CH2 D

C is selected from the group ~onsisting of:

' 1 : _-- CH - CH2 ---- ;

; and, .. .. ,~ .
:~ _ ~ CH2 --_ ~ : combinations thereof.
D is OH, halide, oR4, NH2, NHR3, OM', or OM";
E is the residue of the reaction of at least one Lewis Acid with the D substituent of monomer unit B;

SUBSTITUTE SHEET

W093/00373 210 9 ~ 4 ~a PCT/US92/05454 R1 represents a hydrogen ion (i.e., a proton), a C1-C24 alkyl group (e.g., preferably C1-C12~ more preferably cl-c4), or a C3-c24 cyclo alkyl group;
R2 represents a c1-c24 alkylene group (e.g., C1-C10, more preferably C3-C5), a C3-C2~ cyclo alkylene group, a C6-C18 arylene group, or a C7-C30 alkylarylene group;
R3 represents a C1-C24 alkyl group (e.g., preferably C1-C12, and more preferably Cl-C4), a C3-C24 cyclo~
alkyl group, a C1-C24 aryl group, or a C7-C30 alkylaryl group;
R4 represents a C1-C24 alkyl group (e.g., more typically C1-C12, preferably Cl-C4), a C3-C24 cyclo alkyl group, a C1-C24 aryl group, or a C7-; C30 alkylaryl group;
M' represents alkali metal;
M" represents alkaline-earth metal.

The immobilized catalyst is derived from: a functionalized copolymer having the for~ula - tA]a ~
tB~d ~, wherein A, B and a are defined as above. "d"
represents about 1 to about 99 mole percent and is equal to the sum of b plus c. The functionalized copolymer has a number average molecular weight of from 300 to 10,000,000, preferably 3,000 to 10,000,000, more preferably 3,000 to 3,000,000, yet more preferably

3,000 to 100,000, yet more preferably greater than 5,000 to 10,000 and most preferably greater than 10,000 to 45,000 with a particularly useful and preferred functionalized copolymer having a number average molecular weight of about 35,000.
A particularly preferred immobilized catalyst has a "b" of substantially zero mole percent, and R2 which is a C3 tO C6 alkylene group. The preferred immobilized catalyst is a solid having a particle size SUBSTITUTE SHEET

W093/00373 PCT/US92/0~ ~
2 1 ~ 9 8 4 5 ~ 8 ~sr;~>

of from 0.001 to about 1.0 millimeters and more preferably from 0.01 to about 0.5 millimeters in average diameters.
Another aspect of the present invention relates to a process for using the above immobilized Lewis Acid catalyst. T~e catalysts can be used to produce both high and low molecular weight polymer products, at relatively high reaction temperatures.
In a preferred embodiment of the above prQcess at least one inlet stream comprising- monomer feed to be polymerized is fed to a reactor having at least one discharge stream. The monomer feed is polymerized in the reactor in the presence of the above-described im~obilized Lewis Acid catalyst. The resulting polymerized polymer product is removed from the reactor along with unreacted monomers in the discharge stream while the immobilized catalyst is retained in the reactor.
The present invention includes cationically polymerized polymer product made using the immobilized catalyst o~ the present invention. Such polymers can be made at any suitable molecular weights with preferred rangés being from 300 to 1,000,000, more preferably 300 to 500,000 number average molecular weight. The polymer product preferably has a molecular weight distribution ranging from 1.1 to about 8Ø
However, narrower weight distributions of 1.8 to 3, and preferably 1.8 to 2.5 can be made. The molecular weight and molecular weight distribution can be tailored to particular uses. Useful polymers made using the immobilized catalyst can have number average molecular weights of from 300 to 5,000 and more preferably from 500 to 2SOO for use to mAke materials such as dispersion aids for lubricating oil compositions. Higher molecular weight polymers having a molecular weight of from 10,000 to 100,000, and SUBSTITUTE SHEET

' W093/00373 PCT/US92/054~
2 ~ 4 ~

preferably from 20,000 to 80,000 are useful to prepare viscosity improvers for lubricating oil co~positions.
Yet another ~spect of the present invention relates to a process for alkylating an organic substrate with alkylating agent by contact~ng a mixture of substrate and alkylating agent in the presence of the above described immobilized Lewis Acid catalyst under alkylation conditions.
The substrate to be alkylated can be, for~
example, olefin, alkane, alkyl halides, aromatic, substituted aromatic or multi-substituted aromatic, and mixtures, and the alkylating agent can be olefin, alkane, alkyl halide, aromatic hydrocarbon, hydroxyaromatic hydrocarbon and mixtures; subject to the proviso that the alkylating agent is different from the substrate employed, e.g., if the substrate is an olefin, the alkylating agent is not an olefin.
The present invention also includes a process for manufacturing the above-described immobilized Lewis Acid catalyst. ~In this process functionalized copolymer having mon~mer units represented by the formula: -tA]a-~B]d- is reacted with Lewis Acid catalyst to produce the above-described immobilized Lewis Acid catalyst. A, 8, a and,d are defined above.
- - - ~he immobilized catalysts and processes of the present invention offer a number of advantages over conventional cationic catalysts and polymerization processes.
A significant advantage of such immobilized catalysts is that they can be reused. That is, they are usable for multiple polymerization cycles ~in the context of a batch process) without regeneration, resulting in substantial cost savings, as well as the elimination of significant amounts of hazardous waste typically generated in conventional Lewis Acid processes. Not only can the immobilized Lewis Acid SUBSTITUTE SHEET

W093/00373 PCT/US92/0~4~
~10384~
. ; .

catalysts of the present invention be employed for multiple polymerization cycles, or on a continuous basis for extended polymerization times, but they can also be easily regenerated after they have been deactivated from prolonged use. The catalyst life (before regeneration is required) will depend upon the reaction conditions, and in particular, contaminants present in the feed streams which may poison the immobilized catalyst. In theory, no regeneration sho~ld be needed; however, in practice, poisons are usually present. Surprisingly, even when the immobilized catalysts are partially poisoned, they continue to operate at high efficiencies which are believed to exceed 70%. Not only does this result in significant cost savings, but the environmental impact of the process is minimized.
Another surprising and unexpected advantage of the present invention is that cationic polymerization processes, utilizing the immobilized catalysts, can typically be operated, depending upon the desired molecular weight of the polymer, at relatively higher temperatures, compared to polymerization processes using conventional, but non-immobilized, Lewis Acid catalysts.~ For example, conventional carbocationic polymerization processes for polybutene require temperatures in the range of -10C
to-+10C, to produce polymers having Nn of about 500 to 3,000 reguiring extensive refrigeration systems which are costly to operate. The processes of the present invention can be run at +5C to +3S~C to produce similar molecular weight polymers. Thus, the immobilized Lewis Acid catalyst appears to be more efficient than catalysts of the prior art.
Yet another surprising and unexpected advantage of the present invention is that gaseous catalysts such as BF3 can now be immobilized. It is SUBSTITUTE SHEET

W093/00373 PCT/US92/054~
~la~

now possible to utilize BF3 in a cationic process in a solid form by using the immobilized ~atalysts of the present invention. The benefits of BF3 can now be realized without the hazards and environmental liabilities that are attendant with the use of gaseous BF3. For example, a by-product of gaseous BF3 in a cationic process is HF. Moreover, it is extremely difficult to recycle gaseous BF3 since the BF3 which is separated from a reactor discharge stream contains gaseous monomers which often dimerize or oligomerize during recy~le.
Another advantage of the immobilized catalysts of the present invention is that the catalysts are easy to dispose of in an environmentally advantageous manner. The Lewis Acid catalyst, whic~
typically contains metals, can be stripped from the immobilized catalyst leaving behind a functionalized copolymer, e.g., polyolefin thermoplastic copolymer.
The polyolefin thermoplastic copolymer can then be disposed of substantially without metal contamination.
Another advantage of the im~obilized catalysts of the present invention is that they can be easily removed from reactors. One method of removal involves simply -raising the temperature inside the reactor to a temperature above the melting point of the polymer in which the Lewis Acid is immobilized. The immobilized catalyst then melts and is easily withdrawn from the reactor.
The novel structure of the immobilized catalysts of the present invention can result in enhanced activity for polymerization and lkylation processes when the Lewis Acid catalys , represented by substituent E in the above formula, is separated by at least one carbon atom and preferably more than one carbon (e.g., 4) from the polymer backbone. Without wishing to be bound by any particular theory, it is SUBSTITUTE SHEET

W093/~373 PCT/US92/~
~?>~
21~9845 - - 12 -believed that orien~ation of the active catalyst sites is achieved (under the above situation), in such a manner as to facilitate contact of these sites with the monomer being polymerized. The favorable orientation is believed to result from increased mobility of the active catalyst sites when they are located at the end of a flexible carbon atom or carbon chain. Favorable orientation of catalyst sites enhances polymerization and alkylation activity. The novel structure of the~
immobilized catalysts of the present invention is believed to render each such favorably oriented Lewis Acid catalyst site an active catalyst site. There is little or no interference between neighboring immobilized Lewis Acid catalyst sites. When such interference exists, it can cause the catalysts to effectively "shut-down".
Still another advantage of the Lewis Acid catalysts of the present invention is that they can be used in most polar or non-polar organic solvents. The immobilized catalysts do not require that their use be limited to specific solvents. Useful solvents can include: hexane, heptane, butane,C3-24 hydrocarbyl, and halogenated solvents such as halogenetic hydrocarbons - such as methylene chloride, dichloromethane, ethyl chloride and methyl chloride.
Still yet another advantage of the immobilized c~talysts of the present invention is that they may be regenerated in situ, e.g., in a reactor by washing with an acid and then treating with at least one Lewis Acid reagent.
The regeneration process is quite simple and can be done at relatively low temperatures (even a~bient tempexatures) in the reactor vessel without having to remove the immobilized catalyst from the reactor vessel. It is believed that in situ SUBSrITUTE SHEET

W093/00373 2 1 ~ ~ 8 4 ~ PCT/US92/ ~ ~

regeneration is not practical with Lewis Acid catalysts supported on inorganic substrates because of the number and nature of steps involved.
Yet another advantage of the immobilized Lewis Acid catalysts of the present invention is that minimal amounts of catalyst residues carry over to the polymer product. In comparison to a "once through"
cationic catalyst process, the polymers produ~ed using the immobilized catalysts and processes of the present invention are virtually free of catalyst residues.
The foregoing and other features and advantages of the present invention will become more apparent from the following description.

BRIEF DESCRI~L~
Figure 1: A schematic perspective of the "Brush"
arrangement of chains hydroxylated polypropylene.
Figure 2: 1H NNR spectrum of PIB prepared by catalyst A(PP-O-AlC12) at room temperature. Figure 2A
is a magnified scale (100 times) of the spectrum from 4.0 to 6Ø
Figure 3: lH NMR spectrum of PIB prepared by catalyst C(PB-O-BF2) at 0C. Figure 3A is a magnified scale (100 times) of the spectrum from 4.0-to 6.0 ppm.
Figure 4: 27Al spectrum of an unmobilized catalyst derived from hydroxylated polypropylene and aluminum ethyl dichloride (Example 54).
Figure 4A is a comparative spectrum of the reaction product of l-pentanol and aluminum ethyl dichloride.
Figure 5: 27Al NMR ~pectrum of an unmobilized catalyst derived from hydroxylated polybutene and SUBSTITUTE SHEET

WO93!00373 PCT/US92/~
..
2 1 ~ S

aluminum diethyl chloride (Example 54).
Figure 5A is a comparative spectrum of the reaction product of 1-pentanol and aluminum ethyl dichloride.
Figure 6: 27Al NMR spectrum of an unmobilized catalyst derived from hydroxylated polybutene and BF3 (Example 59). Figure 6A is a comparative spectrum of the reaction product of 1-pentanol and aluminum ethyl dichloride.
Figure 7: Is a schematic diagram of the experimental apparatus of Examples 54-57.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Those skilled in the art will be able to appreciate the present invention by the following detailed description of the preferred embodiments. The present invention relates to an immobilized catalysts and process for preparing such a catalyst. The catalyst is particularly useful in the preparation of a variety of homopolymers and copolymers.
~ -~ The novel immobilized catalysts ~of the present invention can be used to polymerize a variety of monomers into homopolymers and copolymers, e.g., polyalkenes. The monomers include those having unsaturation which are conventionally polymerizable using carbocationic Lewis Acid catalyst polymerization techniques, and monomers which are the equivalents thereof. The terms cationic and carbocationic are used interchangeably herein. Olefin monomers useful in the practice of the present invention are polymerizable olefin monomers characterized by the presence of one or more ethylenically unsaturated groups (i.e., >C=C<);
that is, they can be straight or branched:
monoolefinic monomers, such as vinyl ethers, ethylene, propylene, 1-butene, isobutylene, and l-octene, or .

~ SUBSTITUTE SHEET

W093/~373 PCT/US92/0 polyolefinic monomers. Polyolefinic monomers include cyclic or acryclic, ~onjugated or non-conjugated, dienes.
Suitable olefin monomers are preferably polymerizable terminal olefins; that is, olefins characterized by the presence in their structure of the group >C=CH2. However, polymerizable internal olefin monomers (sometimes referred to in the patent literature as medial olefins) characterized by the presence within their structure of the group C -- C = c -- c can also be used to orm polymer products. When internal olefin monomers are employed, they normally will be employed with terminal olefins to produce polyalkenes which are interpolymers. For purposes of the invention, when a particular polymerized olefin monomer ca~ be classified as both a terminal olefin and an internal olefin, it will be deemed to be a terminal olefin. - Thus, 1,3-pentadiene (i.e., piperylene) is deemed to be a terminal olefin for purposes-of this invention.
Preferred monomers used in the method for forming a polymer in accordance with the present invention are preferably selected from the group consisting of ethylene and alpha-olefins and typically C3-C25 alpha olefins. Suitable alpha-olefins may be branched or straight chained, cyclic, and aromatic substituted or unsubstituted, and are preferably C3-Cl6 alpha-olefins. Mixed olefins can be used (e.g., mixed butenes).
The alpha-olefins, when substituted, may be dir~ctly aromatic substituted on the 2-carbon position ~::1 IR~TI~-I ITF ~HEET

W093/0037~ PCT/US92/0~ ~
~,~
~la~

(e.g., moieties such as CH2=CH-~- may be employed).
Representative of such monomers include styrene, and derivatives such as alpha methyl styrene, paramethyl styrene, vinyl toluene and its isomers.
In addition, substituted alpha-olefins include compounds of the formula H2C=CH-~-X' wherein R
represents C1 to c23 alkyl, preferably Cl to C10 alkyl, and X' represents a substituent on R and C can be aryl, alkaryl, or cycloalkyl. Exemplary of such X' su~stituents are aryl of 6 to 10 carbon atoms (e.g., phenyl, naphthyl and the like), cycloalkyl of 3 to 12 car~on atoms (e.g., cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, and the like) , alkaryl of 7 to 15 carbon atoms (e.g., tolyl, xylyl, ethylphenyl, diethylphenyl, ethylnaphthyl, and the like). Also useful are bicyclic, substituted or unsubstituted, olefins, such as indene and derivatives, and bridged alpha-olef ins of which C1-Cg alkyl substituted norbornenes are preferred (e.g., 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-(2'ethylhexyl)-2-norbor~ene, and the li~e).
Illustrative non-limiting examples of preferred alpha-olef ins are propylene, 1-butene, 1-pentene, lhexene, 1-octene, and 1-dodecene.
Dienes suitable for purposes of the present invention can be straight chain, hydrocarbon di-olefins or cycloalkenyl-substituted alkenes, having about 6 to about 15 carbon atoms, for example:
A. straight chain acyclic dienes, such as 1,4-hexadiene and 1,6-octadiene;
B. branched chain acyclic dienes, such as 5-methyl-1,-4-hexadiene; 3,7-dimethyl-1,6-octadiene;
3,7dimethyl-1,7-octadiene; and the mixed isomers of dihydro-myricene and dihydro-ocinene;

SUBSTITLJTE SHEET

W093/00373 PCT/USg2/0~454 21~98'1~

C. single ring cyclic dienes, such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclo-octadiene and 1,5-cyclododecadiene;
D. multi-ring cyclic fused and bridged ring dienes, such as tetrahydroindene; methyl-tetrahydroindene; dicyclopentadiene; bicyclo-(2.2.1)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene nor~ornenes, such as 5-methylene-2-norbornene, 5-propenyl2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-nor~ornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene;
E. cycloalkenyl-substituted alkenes, such as allyl cyclohexene, vinyl cyclooctene, allyl cyclodecene, vinyl cyclododecene.
of the non-conjugated dienes typicaily used, the preferred dienes are dicyclopentadiene, methyl cyclopentadiene dimer, 1,4-hexadiene, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene.
Particularly preferred diolefins are 5-ethylidene-2-norbornene and 1,4hexadiene.
. The polymer and copolymer product which can be manufactured by the',process of the present invention are those which can be manufactured by a carbocationic polymerization process and include but are not limited to polyalkenes, such as,~polyisobutene, poly (1-butene), polyn-butena, polystyrene, ethylene alpha-olefin copolymers, and the like. The term copolymer as used herein is defined to mean a polymer comprising at least two different monomer units.
, In particular, the immobilized catalysts of the present invention are especiLlly useful for manufacturing polyisobutene, poly(1-butene) and poly-n-butene from feedstreams containing butene monomers. It is especially preferred to use refinery feed streams containing C4 monomers, commonly referred to as Raffinate I and Raffinate II.

SUBSTITUTE SHEET

W093/00373 . PCT/US92/~ ~

21098~5 The Lewis Acids which can be immobilized as described herein to make the catalysts of the present invention are defined herein to include any of those Lewis Acids known in the art to be capable of cationically polymerizing olefins in accordance with conventional techniques, and equivalents thereof.
Suitable Lewis Acids typically include the halides and alkyl compounds of the elements in Column III B and III
A to VI A of the Periodic Table of the Elements~
including alkyl aluminum, aluminum halides, boron halides, transition metal halides, and combinations thereof. It is particularly preferred to use AlRnX3_n (n=0-3) wherein R is C1-C12 alkyl or aryl and X is a halide, for example, Al(C2H5)3~ A1(C2H5)2Cl~
Al(C2H5)C12 and AlC13, 8F3, BC13, FeCl3, SnCl4, SbCl5, AsF5, AsF3, and TiC14.
The preferred catalysts are Lewis Acids based on metals from Group III A, IV B and V B of the Periodic Table of the Elements, including, but not limited to, boron, aluminum, gallium, indium, titanium, zirconium, vanadium, arsenic, antimony, and bismuth.
The Group III A Lewis Acids have the general formula RnMX3_n, wherein M is a Group III A metal, R is a monovalent hydrocarbon radical selected from the group consisting of C1 to C12 alkyl, aryl, alkylaryl, aryl-alkyl and cycloalkyl radicals; n is a number from 0 to 3; X is a halogen independently selected from the group consisting of fluorine, chlorine, bromine, and iodine.
Non-limiting examples include aluminum chloride, aluminum bromide, boron trifluoride, boron trichloride, ethyl aluminum dichloride (EtAlC12), diethyl aluminum chloride (Et2AlCl), ethyl aluminum sesquichloride (Etl.sAlCl1.5), trimethyl aluminum, and triethyl aluminum. The Group IVB Lewis Acids have the general formula MX4, wherein M is a Group IVB metal and X is a ligand, preferably a halogen. Non-limiting examples SUBSTITUTE SHEET

WOg3/00373 PCT/US92/054~

include titanium tetrachloride, zirconium tetrachloride, or tin tetrachloride. The (group V B
Lewis Acids have the general formula MXy, wherein M is a Group V metal, X is a ligand, preferably a halogen, and y is an integer from 3 to 5. Non-limiting examples include vanadium tetrachloride and antimony pentafluoride. The Lewis Acid immobilized in accordance with the present invention will preferably be used during immobilization in gaseous or liquid' form, either neat or as a solution using organic solvents. The Lewis Acid may be used singly (i.e., one particular Lewis Acid catalyst) or in co~bination (i.e., two or more Lewis Acid catalysts).
Typical of Lewis Acid catalysts useful in the practice of the present invention are those h~ving the formula MXm~(R5 )p, as illustrated in the Table, wherein m' = (the coordination of nu~ber of M) - (p' +
l); p~ = O to 3; and, R5 is C1-C12 alkyl, C6-C18 aryl~
C7-Clg alkylaryl, and C3-C15 cyclic or acyclic.

SUBSTITUTE SHEET

WO 93/00373 PCr/US92/0~454 r"' ' ..
2 1 v 9 ~ 4 ~ -- 2 0 TABLE

~m~ 5R5 Lp~

M X ~. ~5 Sb Cl 5 -- 0 Sb Cl 3 -- 0 Sb F 5 ---- 0 Sn. Cl, Br 4 -- o V Cl 4 ---- 0 Be Cl 2 -- o Bi Cl 3 --- 0 Zu Cl 2 ---- 0 Cd Cl Z -- 0 Hg Cl 2 -- 0 As F 3 ---- 0 AS F 5 ---- o Nb F 5 -- 0 Ta F 5 ---- o Ga Cl, Br 3 -- o In Cl, Br 3 -- o Ti Br, Cl 4 -- o Zr Cl 4 -- o W Cl 5 ---- 0 B F, Cl, Br, I 3 -- o Fe Cl, Br 3 -- o Al Cl, Br, I 3 -- o Al Cl, Br, I 3 C1 to C12 alkyl, 0-3 aryl, alkylaryl, cyclic or acyclic Lewis Acids useful as catalysts in carbocationic processes as well as carbocationically polymerizable monomers, and, the polymers produced from such processes are disclosed and described in the following publications: 1) Cationic Polymerization of SUBSTITUTE SHEET

W093/00373 PCT/US92/0~ ~
2 ~ ~ 3 8 ~

Olefins: A Critical Inventory, Kennedy, Joseph P., John Wiley & Sons, New York (1975), and, 2) Carbocationic Polvmerization, Kennedy, Joseph P., John Wiley, & Sons, New York (1982).
The immobilized Lewis Acid catalysts of the present invention may be used singly or in combination with cocatalysts. The cocatalysts include materials known in this art such as water, alcohols, Bronsted Acids, for example, anhydrous HF or HCl, and alkyl halides, for example, benzyl chloride or tertiary butyl chloride.
The immobilized catalysts of the present invention are derived from polymers, preferably polyolefin thermoplastic copollmers, having functionalized monomers incorporated into the structure thereof. Such functionalized copolymers can be represented by the following structural formula:

-tA]a--t~]d--. .
wherein "A" represents unfunctionalized monomer unit, and "B" represents the functionalized monomer unit in the copolymer wherein:
Rl -A is ~ CH2 - CH ~

R1 which can be the same or different represents a hydrogen ion (i.e., a proton), an alkyl group, preferably a C1-C24 alkyl group, and more preferably C1-C4 alkyl group, .

SUBSTITUTE SHEET

2 1 ~ 4 5 ~ PCr/U~92J0~ t - 2~ -or a cyclo alkyl group, preferably a C3-C24 cyclo alkyl group, and morepref erably C5-C8 cyclo alkyl group;
and, B = ~ C~ - C~

herein D, which represents the functional portion of monomer unit B, can b~ OH, halide, NH2, oR4, NHR3, OM', or OM"
R2, which can be the same or different represents an alkylene group, preferably a C1-C24 alkylene group, more preferably a C3-C5 alkylene group, a cyclo alkylene group, preferably a C6-C24 cyclo alkylene group, an arylene group, preferably, a C6-C18 arylene group, or, an alkarylene group, preferably a C7-C
alkylarylene group, R3, which can be the same or different represents an alkyl group, preferably a Cl-C24 alkyl group, preferably a C1-C4 alkyl group, a cyclo alkyl group, preferably a C3-C24 cyclo alkyl group, more preferably a C5-C8 cyclo alkyl group, an aryl group, preferably a C6-C18 aryl group, or, an alkaryl group, preferably a C7-C30 alkaryl group;
R4, which can be the same or different represents an alkyl group, preferably a SUBSTITUTE SHEET

W093/00373 P~T/US92/054~
2 ~ t3~A~

Cl-C2~ alkyl group, more preferably a Cl-C4 alkyl group, a cyclo alky group, prefera~ly a C3-C~4 cyclo alkyl group, an aryl group, preferably a C6-clg aryl group, or, an alkaryl group, preferably a C7-C3~ alkylaryl group;
a and d represent the mole % of each respective monomer unit A and B in the functionalized copolymer with "d"
representing the sum of b and c in formula III below, the sum o a~d being 100 mole %;
M' represents alkali metal;
M" represents alkaline-earth metal.

The functionalized copolymers are typically prepared from borated copolymers.which are then treated to replace the boron with functional groups represented by D in formula I in the following manner. Nore spec~fically, sufficient amounts Si.e., sufficient to eventually yield the desired amounts and ratios depicted by a, b, and c, in formula III below) of suitable alpha-olefin mono~ers (A) and suitable borane ~onomers (B) (as defined hereinafter) can be reacted in a suitable reactor using ~iegler-Natta catalysis under sufficient reaction conditions effective to fo~m a borated, preferably thermoplastic, copolymer. The Ziegler-Natta polymerization may be catalyzed with conventional Ziegler-Natta catalysts or equivalents thereof such as TiC13 AA/Al(Et)3 or a transition metal halide of Groups IV to VIII of the Periodic Table of the Elements and a cocatalyst which is an alkyl compound including alkyl halides of a metal of Groups I
to III of the Periodic Table of the Elements and the like. The abbreviation "AA" used herein is defined to mean "alumina activated". Activated aluminas are .~IIR~TI~ rrE S H E ET

W093/00373 PCT/US9 /~
2~U9~

widely known and used in adsorption and catalysis because of their large surface area, pore structure, and surface chemistry. They are made by the controlled heating of hydrated aluminas. The activated alumina can be used as a catalyst support. The use of activated alumina as a catalyst support is optional.
Non-limiting examples of the unfunctionalized monomer (A) alpha-olefin monomers which may be used to prepare the functionalized copolymer intermediates uséful to make the immobilized catalysts of the present invention include ethylene and C3-C24 alpha-olefin monomers, such as, propylene, l-butene, l-pentene, 1-hexene, oligomers, co-oligomers, and mixtures thereof.
Mo~t preferred are propylene and l-butene, the alpha-olefin monomers include any monomer, oligomer or co-oligomer polymerizable by Ziegler-Natta catalysis and equivalents thereof.
Suitable borane monomers, from which monomer unit B in formula I is derived, can be prepared by reacting a diolefin having the formula CH2=CH-(CH2)m-CH=CH2 (wherein m is- about 1 to 10) with `a dialkyl borane solution. Non-limiting examples of diolefins include 1,7-octadiene, 1,5-hexadiene, and 1,4-pentadiene. Non-limiting examples of dialkyl borane -solutions include 9-borabicyclot3,3,1~nonane (herein-after abbreviated as "9-BBN") in tetrahydrofuran, ethyl ether, -methylene chloride, and the like. Borane monomers, useful in the practice of the present invention, and methods of preparation, are disclosed in U.S.~ Patent Numbers 4,734,472 and 4,751,276 which are incorporated by reference. Preferred borane monomers useful in the practice of the present invention will have the following formula:

~lJBSTlTUTE SHEET

W~93/00373 PCT/US92~054~
2~3~ 3 ~ ~

R~
(II) CH2 = CH - (CH2)n ~ B
\R7 where n = about 3 to 1~ and R6 and R7 are the same or different and are alkyl or cycloalkyl groups having about 1 to 10 carbon atoms. Non-limiting examples of borane monomers include B-7-octenyl-9-BBN, B-5-hexenyl-9-BBN, B-~-pentenyl-9-BBN and the like with the most preferred being B-5-hexenyl-9-BBN.
The borated copolymers, preferably thermoplastic copolymers, are functionalized prior to reacting with a Lewis Acid catalyst in order to form the functionalized copolymer from which the immobilized catalysts of the present invention are derived.
It is desireable to functionalize the borated polymer so that the catalyst can be chemically bonded to it. However, if one were willing to accept the attendant disadvantages, the borated copolymer may be reacted directly with Lewis Acid catalyst to form an immobilized catalyst. The functional groups include halides, hydroxyls, carboxylic acid, NH2 and materials ;having the formula oR4 and NHR3, wherein R3 and R4 are as defined in formula I. It is especially preferred to utilize primary functional groups such as hydroxide and halides. The preparation of the functionalized copolymers of the present invention is typically accomplished by replacement (referred to herein as conversion) of borane groups in the borated copolymex with the group~. represented by substitu~nt D in formula I by contact with a conversion agent. Suitable conversion agents include hydrogen peroxide/NaOH, NH2Cl, NH2S03H, NaI/chloramine-t-hydrate/CH3C02Na. It is particularly preferred to use hydrogen peroxide/NaOH
when the desired functional group is hydroxyl, this ~1 IR~rl~l rrF .~ H F FT

W093/~373 P~T/US92/054~ ~
21~98~5 latter embodiment being most preferred. The conversion agent and conversion conditions are selected to cleave the boron group from the borated thermoplastic and substitute a functional group in its place. The extent of conversion is determined by the eventual valves of c and b of formula III sought to be impacted to the immobilized catalyst.
Optionally, the functionalized copolymer intermediates of the present invention may be further reacted with an alkyl alkali metal or alkyl alkaline-earth metal compounds to form an alternative functional group more easily reactable with certain Lewis Acids s~ch as BF3, prior to reaction with a Lewis Acid catalyst. These alternative functional groups are depicted in formula I when D is OM' or OM".
Examples of alkyl alkali metal and alkyl alkaline-earth metal compounds include butyl lithium, butyl sodium, butyl potassium, and ethyl magnesium. In general, the alkyl alkali metals will have the formula M'R' wherein M' is an alkali metal and R' is a Cl-C24 alkyl grou~. The alkali metals (Group I A of the Periodic Table) include ~ithium, sodium, potassium, rubidium, cesium and francium. In general the alkyl alkaline-earth metal compounds will have the formula M"R'' wherein M" is an alkaline-earth metal and R" is a Cl-C24 alkyl group. The alkaline-earth metals (Group II A of the Periodic Table of the Elements) include calcium, barium, magnesium, strontium and rhodium.
Thus, the term functionalized copolymer as used herein is intended to include functionalized copolymers which are further reacted with an alkyl alkali or alkaline-earth metal compounds.
A stoichiometrically idealized reaction sequence for the preparation of a completely functionalized copolymer (i.e. b -> 0) from alpha-olefin monomers (A) and borane monomers (B), e.g., a SUBSTITUTE SHEET

WOg3/00373 PCT/US92/054~
2 1 ~ 5 functionalized copol~mer derived from propylene and having a borane monomer having units completely reacted to have hydroxyl functionality or halide functionality, is as follows:

a CH2 = CH + d fH2 = CH
CH3 (IH2)4 B
R R

1 TiC13AA/Al(Et)3/toluene (CH2-fH)a-(CH2-fH)d CH3 (C1~2)4 R R

NaOH/N202 ~ "or" ~ aI/Chloramine-T-hydrate/CH3C02Na : , , " ,(CH2-fH)a-(CH2-lcH)c , (cH2-cH)a-(cH2-lH)c CH3 (IH2)4 CH3 (IH2)4 OH

The term "AA" has been previously defined to mean alumina activated.
. The functionalized copoly~ers are typically :~ synthesized to be insoluble in common organic solvents at room temperature and stable under typical cationic polymerization conditions. The functionalized copolymers will typically have a number average molecular weight (~n) in the range between 300 to ~ 1 IR~C;TITLJTE SHEET

WO 93/00373 PCr/US92/05454 r~.
21038~ 28-.
lo,ooo,ooo, preferably 3,000 to 3,000,000, more preferably 3,000 to 1,000,000, yet more preferably greater than 3,000 to 100,000, even more preferably greater than 5,0oO to 50,000 and most preferably greater than 10,000 to 45,000, with a particularly useful and preferred functionalized copolymer having an ~Mn) of about 35,000.
The immobilized catalysts of the present invention will typically be prepared from the functionalized copolymer in the following manner.
A suf f icient amount of at least one Lewis Acid catalyst, preferably in excess, is mixed with a suf f icient amount of a functionalized copolymer in a suitable reactor vessel under suitable reaction conditions effective to react the functionalized copolymer with the Lewis Ac~d catalyst thereby producing the immobilized catalyst as de~ined in formula III. By "excess" is meant a molar ratio of Lewis Acid catalyst to functional groups of about more than 1:1, preferably 5:1. The reaction is preferably carried out at a temperature of about 20C to 1~0C
although the reaction temperature may range from about -50C to 200C. The reaction is preferably carried out by dissolving the Lewis Acid catalyst in a thoroughly dried, inert solvent selected from any suitable solvents including alkanes, aromatic solvents and alkyl halides, however, the Lewis Acid catalyst may be in the gas phase or liquid phase when reacted with the functionalized copolymer. The preferred solvents will be good solvents for the Lewis Acid catalyst and will also be relatively good solvents (swellable) for the polymer substrate to maximize the penetration of reagent into the polymer matrix. Immobilized catalysts are not readily extractable by the solvent and by reaction media.

SUBSTITUTE SHEET

W093/00373 PCT/US92/054~
2109'~

The resulting immobilized Lewis Acid catalysts of the present invention can be described as comprising polymer having at least one Lewis Acid immobilized within the structure thereof, said polymer having monomer units represented by the structural formula:

(III) ~~tA]a~~~B]b~~tC]c~~

wherein a + b + c represents the respective mole % of monomer units A, B, and C in said polymer with the sum of a+b+c preferably being about 100%, and wherein a represents about l to about 99 mole %
b represents about 0 to about 50 mole %
c rei~resents about 1 to about 99 mole %
A, B, are as described in connection with formula I;
C is selected from the group consisting of:

tIV) - . -_ ~ CH

E

v) r - _ - CH - CH2 _ O
E ; and combinations thereof.

SUBSrITUTE SHEET

W093/~373 PCT/US~2/054~
21~8~

wherein:
E is the residue of the reaction of a Lewis Acid with the D functional substituent in mono~er unit B; and R2 is as described in formula I.

When monomer Unit B in f ormula I remains unconverted, the D substituent remains unchanged and monomer unit ~ in ~ormula I becomes monomer unit ~'in formula III. In contrast, when D in monomer unit B is acted upon by ~he conversion agent, monomer unit B
becomes monomer unit C ~y replacement of substituent D
with su~stituent E (i.e., the Lewis Acid residue).
As indicated above, E is de~ined as being t~
residue of the reaction of a Lewis Acid Catalyst with the D functional group of monomer unit B. It will be appreciated by those skilled in the art that the precise formula for E will vary depending upon the Lewis Acid catalysts used and the functional groups present on the functionalized copolymer.
The ratio of a:c in formula III will typically be about 1:1 to about 100:1, more typically about 5:1 to about 100:1, and preferably about 20:1 to about 50:~. The ratio of b:c will typically be about O.1:1 to about 20:1, more typically about 0.1:1 to about 10:1, and preferably a~out 0.5:1 to about 5:1.
Where all of the D reacts to form E, than b becomes 0.
In a preferred embodiment substantially all of the D is reacted to form E.
Although the immobilized catalysts of the present invention comprise a Lewis Acid chemically reacted with and chemically bonded to a copolymer backbone, there is at least one instance wherein the bond is a pi (~) complex. Specifically, when D is hydroxyl and the Lewis Acid intended to replace D is SUBSTITUTE SHEET

WO 93/00373 PCI/US92/0~
21~338'15 BF3, then the BF3 will form a pi (-r) bond with the copolymer backbone by complexing with hydroxyls contained in the copolymer.
The i~mobilized Lewis Acid catalysts of the present invention will typically have, prior to any processing, a particle-like structure wherein each particle consists of an immobile copolymer backbone and substituent Lewis Acid. While not wishing to be bound to any particular theory, it is believed that the ~ewis Acid tends to predominate on the surface of the particle, while the interior of the particle will tend to consist primarily of immobile crystalline copolymer.
More specifically, when the borated copolymer intermediate is prepared prior to forming the functionalized copolymer, the difference in reactivity between the borane comonomer (lower activity) and olefin comonomer (higher activity) is believed to result in a predominantly block or sharply tapered copol~mer. It is believed to be i~portant that the non-boron containing block be crystalline, since as the block crystalizes, it forms a particle ha~ing a crystalline core. During crystallization the boron monomer block migrates or ~orients at the particle surface, thereby ensuring eventual predominance of the Lewis Acid sites at the surface of the particle. This orientation phenomena is maintained even upon melt extrusion of the immobilized catalyst and becomes even more pronounced in the final catalyst due to the high polar character of the Lewis Acid. This structure results in catalysts having good polymerization activity and high surface area. Reference is made to Figure I showing the formula and speculated morphologic arrangement of hydroxylated polypropylene.
The immobililzed catalysts of the present invention may be used for prolonged periods of time and then regenerated. The catalyst may even be regenerated ,c;l IR~TITlJTE SHEET

W093/00373 PCT/US92/0~ ~

21~4~ - 32 -in situ în a reactor if so desired. The catalysts are easily regenerated. The regeneration process is preferably accomplished by first washing the immobilized catalyst while in the react~r vessel with any Bronsted acid such as HCl, H2So4 and the like, and then treating the immobile, plastic phase of the immobilized ~atalyst with Lewis Acid reagents.
Optionally, after the acid wash, and prior to treatment with the Lewis Acid rea~ent, the immobilized catalyst is treated with an alkyl alkali metal or an alkyl alkaline-earth metal compound to form an intermediate salt which is then treated with Lewis Acid catalyst reagent. Typically, these Lewis Acid reagents will consist of Lewis Acid catalyst solutions in organic solvents such as tolue~e, methylene chloride and the like. Preferably the strengths of the Lewis Acid catalyst solution will range from about 10 wt.% to about 50 wt.~. It is preferred to use an excess of Lewis Acid catalyst reagent in the regeneration process. By "excess" is meant from two to five times the mole ratio of catalyst to functional groups.
Rather than use solutions of Lewis Acid c~talysts, the Lewis Acid catalyst may be used in a liquid or gaseous form.
The immobile thermoplastic is stable under cationic reaction conditions; it is insoluble in hydrocarbon solvents below 500C and has high mechanical strength. One particularly preferred f orm of the immobilized catalyst is f inely divided particles. The finely divided particles can be obtained using various particle size reduction proceæses including freezing and pulverizing, and conventional particle size reduction processes.
While the polymer backbone of the immobilized catalysts of the present invention can exist as random copolymers, block copolymers, tapered copolymers, graft SUBSTITUTE SHEET

W093/~373 PCT/USg2/~
21~3~ l;..

copolymers and alternating copolymers, it is particularly preferred to use immobilized catalysts of the present in~ention having a monomer distribution which is described as block or predominantly tapered.
It will be appreciated by those skilled in the art that the monomer configuration of the copolymer will affect its chemical and physical properties. The term copolymer as used herein is defined to mean a polymer having two or more monomeric units. The monomeric configuration in the polymer backbone is determined by a number of factors well known to those skilled in this art, including reactivity ratios, rates of monomer addition, sequencing, reactor design, reaction conditions and the like.
As indicated above, it is believed to be highly advantageous that the immobilized catalysts of the present invention exhibit crystallinity. The degree of crystallinity is directly related to the molar amount "a" of the monomer component ~A] of formula I. Because of the advantages of crystallinity, it is desired to select monomer type and polymerization conditions conducive to the formation of thermoplastic copolymer.
Typically the value of "a" will range from about 1 to 99 mole %, more typically about 25 to 99 mole %, and preferably about 50 to 99 mole % of the iD obilized catalyst backbone. It will be appreciated by those skilled in this art that the degree of crystallinity will increase with increasing mole ~ of tA~. It will also be appreciated that the physical characteristics of the immobilized catalysts of the present invention will be related, at least in part, to their degree of crystallinity. For example, a mole %
of [A] greater than 50~ will typically result in a solid phase i~mobilized catalyst.

SUBS I ITUTE SHEET

W0~3/00373 PCT/US92/~54 09P~ 34 -There are various methods of determining when the desired crystallinity of the immobilized catalysts of the present invention is achieved. One indirect method is to react the boron in the boron-containing copolymer ~prior to functionalization) with a Lewis base. The weight increase is indicative of the amount of bcron present and the amount of thermoplastic monomer units ~A] present in the copolymer may then be calculated. As previously mentioned, when the mo~e ~
of ~A] is about 50% or greater, the immobilized catalysts will exhibit desired crystallinity. In addition to the mole % of [A~, the crystallinity is a function of the amount of boron sites on the surface which can be functionalized to react with a Lewis Acid catalyst (i.e., an increase in the borated precursor of ~onomer unit B will decrease the amount of monomer unit A in the polymer). The number of surface boron sites can be measured by a variety of conventional analytical techniques. It is preferred to use Boron NMR. In a preferred em~odiment, most of the Lewis Acid catalyst reactable sites depicted by D in formula I will be on the surface of the functionalized thermoplastic copolymer.
One particularly preferred method of determining crystallinity is -to measure the DSC
(Differential Scanning Calorimetry) curve of a sample of the immobilized Lewis Acid catalyst. This will give the melting point of the sample, and, from the intensity of the peak of the curve, the crystallinity can be calculated.
Access to any boron which may be present in the interior of the precursor copolymer particles by the conversion agent is controlled by using swellable solvents such as THF. By swellable solvents is meant a SUBSTITUTE SHEET

W093/00373 P~T/US92/0~4 solvent which will diffuse into a functionalized copol~mer. Examples of such solvents include methylene chloride and toluene.
As previously mentioned, it is believed that, more likely than not, the crystalline segments of the immobilized catalysts of the present invention tend to form an inner immobile crystalline phase while the Lewis Acid sites and any other functionality which may be present tend to be oriented at the particle sur~ace.
Thus, the immobilized catalyst retains at least some of the original physical properties of a pure crystalline polymer. For example, the crystallinity and thermal stability of an immobilized ~atalyst of the present invention will be similar to that of the purely thermoplastic crysta}line copol~er.
In addition, as previously mentioned, the immobilized catalyst of the present invention may be used in particle form. Typically, in a polymerization reaction the particle size of the immobilized catalyst -will be about 0.001 mm to about 20.0 mm, more typically about 0.01 mm to about 10.0 mm, and preferably about 0.01 mm to about 1.0 mm.
- The catalyst can be formed to fine particles by~ suitable means. Preferably, the catalyst can be frozen by suitable means, such as liquefied compounds which are gaseous at ambient temperature such as nitrogen. The fr~zen catalyst can be comminuted to a fine particle size, preferably having a distribution of from about 0.001 mm to about 1.0 mm and more preferably from about 0.01 mm to about 0.5 mm. It has been found that the use of catalyst in the preferred range results in polymer of the present invention having greater terminal unsaturation and thereby greater reactivity.
Particularly preferred polymer having greater terminal unsaturation are polybutenes including poly-n-butenes and polyisobutylene.

C:l IQ~::TITI ITF .C:I-IFFT

W093/00373 PCT/US92/054 ~

~, ~
- 2 ~ 5 The catalyst may be processed according to conventional thermoplastic processing techniques such as molding, extruding, forming and coating to produce various catalyst structures having optimal surface areas. The catalysts may be molded into various shapes such as column packing rings and the like. It is contemplated that the catalysts of the present invention can be coated onto a variety of supporting substrates such as metal, ceramic, plastics including thermoplastic, glass, fiberglass, carbon, graphite and the like. It is further contemplated that these catalysts can be extruded or molded onto such substrates.
In a typical molding process, the immobilized catalyst is fed to a molding machine having a heating means and cooling means. The immobilized catalyst is heated to a state where it is flowable (e.g., at or above glass transition temperature) and it is transported by the feed means to a mold having cavities therein. The plastic~is transported under sufficient heat and pressure to fill in the cavities, cooled, and removed, thereby retaining the shape of the cavities.
The coatings may be any conventional coating and equivalents thereof including, ;but not limited to, liquid polymer melts or solution polymer coatings. The coatings may also comprise dispersions, both aqueous and nonaqueous, enamels, lacguers, dry powders, and aqueous or organic electrodeposition compositions. The coatings may be cured in conventional manners including heating, drying, crosslinking, and radiation. The coatings will contain conventional components and incipients such as solvents, resins, binders, dispersants and optionally pigments, mixing and flow agents, curing agents and the like. The coatings are prepared using conventional mixing, dispersing, and ~:1 JRSTITUTE SHEET

W093/00373 PCT~US92/054~
--~ 2 ~ ~ 3 8 ~ ~
.

particle ~ize reduction processes and equipment such as stirred tanks, ball mills, shot mill, high shear mixers and the like.
It is contemplated that the surfaces of reactor vessels and process piping and equipment may be coated with the immobilized catalysts of the present invention. In addition, reactor components such as packing may be coated. Any conventional coating processes and equivalents thereof nay be used including, but not limited to, spraying, dipping, powder coating, brushing, rolling, electrodeposition and the like.
Coatinqs, manufacturing processes, application processes, and, plastics processing methods, produc~s and process equipment are disclosed in Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, John Wiley & Sons, New York (1982).
The carbocationic polymerization process of the present invention may be carried out as a continuous, semi-continuous or batch process. The " reactors which may be utilized in the practice of the present invention include conventional reactors and equivalents thereof such as batch reactors, stirred tank reactors, fluidized bed reactors, and continuous i tank or tubular reactors and the like. As previously mentioned, the process may be continuous, batch or semi-continuous and combinations thereof.
The reactor will contain sufficient amounts of the immobilized catalyst of the present invention effective to catalyze the polymerization of the monomer containing feedstream such that a sufficient amount of polymer having desired characteristics is produced. The reaction conditions will be such that sufficient temperature, pressure, and residence time are maintained effective to produce the desired polymers having the desired characteristics.

Cl IQ~ TITI ITF ~FFT

W093/00373 PCT/US92/0~4 ~
21~8~

Typically, the catalyst to monomer ratio utilized will be those conventional in this art for carbocationic polymerization processes. In the practice of t~e present invention, the catalyst to monomer ratio is selected based on the ratio of residue E to monomer being polymerized. In the practice of the present invention the mole ratio of the residue E to the monomer will typically be about 1/5000 to about l/50, more typically about 1/1000 to about 1/100, and preferably about 1/500 to about 1/200. This mole ratio will be calculated by determining the number of Lewis Acid catalyst sites in the immobilized Lewis Acid catalyst. This can be done by using conventional analytic testing techniques such as elemental analysis, NMR (e.g., aluminum NMR) and absorption spectroscopy.
Once the number of Lewis Acid sites per unit of immobilized catalyst is known, the mole ratio is calculated in a conventional manner.
The reaction temperature will typically be maintained to about 50C to about -30C, more typically about 40C to about -20C, and preferably about 30C to about -10C. The reaction pressure will typically be about 200 k PA to about 1600 k PA, more typically about 300 to about 1200, and preferably about 400 to about 1000. The degree of polyitierization of the monomer feedstream will typically be about 6 to about 10,000, more typically about 10 to about 2,000, and preferably about 10 to about 500.
The yield of polymer is dependent on reaction time and catalyst particle size. The cationic polymerization of a polymer such as isobutylene is related to the availability of catalyst group (i.e. E).
The larger the immobilized catalyst particle, the smaller the surface area of the catalyst which is available. Small surface areas, preferably less than 1 millimeter diameter particles are preferred for ~C;l IRSTITIJTE SHEET

W093/00373 PCT~US92/054 increased reaction rate. NeverthelesS, the extent of reaction will continue to be high but with larger particles with the total reaction taking a longer period of time.
The molecular weight of the polymer produced, preferably a polybutylene using a polyolefin immobile catalyst of the present invention has been found to be higher than using the corresponding Lewis Acids from which the immobilized catalysts are derived. Fdr example, conventional Lewis Acids such as AlC13, ethyl aluminum dichloride, diethyl aluminum chloride, and boron trifluoride used as catalysts for the reaction of polybutenes results in lower molecular weight polymer than if they are immobilized. While not wishing to be bound to any theory, it is speculated that the relatively higher molecular weight of polymer made using the immobilized catalyst of the present invention may be due to slow chain transfer because of stable carbocation in the immobilized catalyst. The alkoxide ligand denotes ~-electron density to aluminum active site and stabilizes the propagatin~ center. This affect is very significant for catalysts having a immobilized structural unit of -0)2AlEt species. As illustrated in the examples specific immobilized catalysts having at least -some immobilized structure of aluminum ethyl or aluminum` diethyl result in higher molecular weight polymer. Therefore, the molecular weight of the polymer of the present invention depends on temperature, solvent type, and catalyst type.
A preferred combination of higher temperature and specific catalyst structure derived from a diethyl aluminum or triethyl. aluminum type catalyst and a polar solvent results in higher molecular weights. A
preferred immobilized catalyst to achieve higher molecular weights is one using a polar solvent such as methylene dichloride, at a temperature of greater than ~;lJRSTlTUTE SHEET

W093/00373 PCT/US92/0~ ~
2 1 ~ 5 -45C and preferably greater than -20C and most preferably at a temperature range of -30 to +10C. An immobilized ~atalyst can be derived from a dialkylhalide Lewis Acid. Diethyl aluminum chloride is preferred. Polymer using these pre~erred featuxes have a mol(Bcular weight of greater than 10,000 and preferably greater than 20,000 number average molecular weight.
In specific embodiments of the present invention cationically polymerized polymer having controlled and increased terminal unsaturation can be produced.
Figure 2 shows the lH NMR spectrum of polyisobutylene lPIB) which was prepared by using immobilized AlC13 wit~ a copolymer of propylene and 1-hexenyl-6-ol (PP-0-AlC12) at room temperature. The overall spectrum is similar to those of found PIB
prepared by soluble Al catalysts, such as AlC13, EtAlC12, Et2AlCl, as well as C5-0-AlC12 (1-hexenyl-6-AlC12) catalyst. Two major peaks are at 0.95 and 1.09 ppm, due to -CH3 and -CH2 protons in PIB polymer. There are some weak peaks located in the olefinic region, between 4.5 and 6.0 ppm. The unsaturated double bond in polymer chain is the evidence of proton chain transfer reaction during the polymerization. In conjunction with the gel permeation chromatography (GPC) molecular weight studies, the integrative intensity of olefinic region implies an average a double bond per polymer chain. In detail, (Figure 2A), there are two quartets at about 5.4 and 5.2 ppm and two singlets at about 4.9 and 4.6 ppm. The singlets at 4.9 and 4.6 ppm are indicative of two types of nonequivalent vinylidene hydrogens which may be located at the end of polymer chain. The quartets at 5.4 and 5.2 ppm are the olefinic SUE~STITUTE SHEET

W093/00373 PCTtUS92/~
2 1 ~

hydrogens coupled to methyl group, which are due to the internal double bonds. The lH NMR peak assignments are summarized in Table I.

Table I, Olefin Structures from lH NMR Sh~f~s structure Observed lH Chemical Shifts -C~ -C-C=C 4.88, 4.66 singlet C
lC lC
-C~ -C--C-C 5.15 singlet -C~ -C~ -C-C-C 5.18 quartet C C\

-C ~ 5.38 quartet C ?C

A significantly high amount of internal double bonds with various structures are present, which indicates carbocationic isomerization taking place by Lewis acid catalyst after the polymerization reaction.
This olefin isomerization behaviors are similar to those in the soluble Al catalyst systems, such as AlCl3 EtAlC2, Et2AlCl.
A different lH NMR spectra of PIB was observed by using immobilized catalyst BF3 with a copolymer of butene-l and 1-hexenyl-6-ol (PB-Q-BF2) at 2S a~d 0C. The chemical shifts in double bond region consist of two major singlets at 4.9 and 4.6 ppm, ~IIR STIllUrrE SHE ET

W093/00373 PCT/VS92/O~i~i ,/so~
21{)~8~5 - ~

corresponding to terminal double bond, and two small peaks at about 5.15 ppm, corresponding to internal double bond. (Figures 3, 3A) Comparing the integrated intensities between olefinic peaks, shown in Figure 3(A), the PIB prepared at 0C contains more than about 85% of terminal double bonds than internal double bonds. The reason for such a high percentage of terminal double bonds in PB-0-8F2 polymerization is not clear. The proton transfer reaction (B-proton elimination~ is the termination step which can form both terminal and internal double bond as shown in the following equation.

~3 ~PIB--cH2-Ç+ A-~H3 proton chain transfer ~H3 ~H3 PIB - CH2-c=cH2 + - PIB--CH=C-CH3 The elimination of proton from two terminal methyl groups are statistically favorable. However, the elimination of proton from the last methylene unit forms a thermodynamically stable internal double bond.
Theoretically, the maximum percentage of terminal double bonds in the final PIB can not be more than 75%.
It is speculated that some effects from the substrate polymer may play a role to control the termination reactioris and to avoid any i~omerization reactions. A
control experiment, using Cs-O-BF3 (1-hexenyl-6-BF2) :

SUBSTITUTE SHEET

WOg3/00373 PCT/US92J054~
.. ..
~3~S

soluble catalyst under the same reaction condition, resulted in more than 30 mole percent of internal double bonds.
The PIB product with high concentration of terminal double bonds is a very desirable molecular structure, called "reactive PIB", which can be easily functionalized under mild reaction conditions. The terminal double bonds react more easily with maleic anhydride than the internal double bonds. Internal' unsaturated PIB preferably undergo a halogenation reaction before maleic anhydride reaction. Known "reactive PIB" here a low number average molecular weight (500-2000 g/mole) PIB with 60-70% terminal (or external) double bonds, which is prepared by ~F3 catalyst. Reference is made to U.S. Patent No.

4,605,808 hereby incorporated by reference for a review of the reactivity of terminal unsaturation. The polymer of the present invention, preferably PIB, preferably contains at least 60, preferably at least 70, more preferably at least 8 percent of terminal double bonds.
The feedstock stream to this process may be at least one pure or mixed monomer feed~tream or combinations thereof. Additionally, the monomer feedstream may be mixed with solvents such as hexane, methylene dichloride and the like. A preferred feedstock to this process may be a pure or mixed refinery butene stream containing one or more of 1-butene, 2-butene (cis and trans), and isobutene. The preferred feedstocks (preferred on an availability and economic basis) are available from refinery catalytic crackers and steam crackers. These processes are known in the art. The butene streams typically contain between about 6 wt.% and about 50 wt.% isobutylene together with 1-butene, cis- and trans-2-butene, isobutane and less than about 1 wt.~ butadiene. One S~JBSrlTUTE SHEET

WOg3/~373 PCT/US92/~

21098~ 44 _ .
particularly preferred C4 feedstream is derived from refinery catalytic or steam cracking processes and contains about 6-45 wt.% isobutylene, about 25-35 wt.%
saturated butanes and about 15-50 wt.% 1- and 2-butenes. Another preferred C4 feedstream is referred to as Raffinate II characterized by less than about 6 wt.%
isobutylene. The monomer feedstream is preferably substantially anhydrous, that is, it contains less than so ppm, and more preferably less than about 30 ppm, and most preferably less than about lO ppm, by weight of water. Such low levels of water can be obtained by contacting the feedstream, prior to the reactor, with a water absorbent (such as CaCl2, CaS04, molecular sieves and the like) or by the use of distillation drying.
Suitable molecular sieves include 4 to 8 US mesh 3 An~strom molecular sieves.
The monomer feedstream is typically substantially free of any other impurity which is adversely reactive with the catalyst under the polymerization conditions. For example, the monomer feed to an immobilized catalyst should be preferably substantially free of b~ses (such as caustic), sulfur-containing ~ compounds (such as H2S, COS, and organomercaptans, e.g., methyl mercaptan, ethyl mercaptan), N-containing compounds, and the like. Most ~preferably, the monomer feed contains less than about ppm by weight of sulfur-containing compounds, calculated as elemental sulfur, less than about 10 ppm by weight of N-containing compounds (calculated as elemental N), and less than about 10 ppm by weight of caustic, calculated as NaOH. Such low levels of base, sulfur and nitrogen impurities can be obtained by conventional techniques, as by the use of caustic to remove sulfur- and nitrogencompounds from a refinery C4 stream, followed by water washing to remove caustic, drying with any of the above water absorbents, SUBSTITUTE SHEET

W093/00373 PCT/US92/~
2:~09~ 1~
- 4s -hydrogenating to remove c4 -c5 diolefins te.g., butadienes) (to a level of below 1 wt. ~, preferably <1, 000 ppm by weight) and cooling the resulting purified C4 stream for feed to the tubular reactors of the present invention, after admixing the selected cocatalyst therewith.
The monomer feedstream is typically substantially free of aromatic compounds, such as benzene, toluene, xylene, naphthalene and other aromatic solvents (e.g., <lo ppm aromatic compounds) to avoid the resultant reactive degradation of the immobilized catalyst. Therefore, use of an aromatic solvent is not envisioned in this process.
It is contemplated that this process may be used to polymerize and copolymerize various monomers from pure or mixed feedstreams such as isobutenes from pure or mixed streams (containing other butenes); n-butenes from streams containing small amounts of isobutenes (e.g., less than about 5 wt.%); and sequentially isobutene from a mixed stream, and then n-butenes. It is also contemplated that this process may be used to copolymerize various monomers including 1-butene, ethylene and hexane.
; Other design parameters such as recycle rate -and % diluents are matters of choice in this instance and may be readily determined by one having ordinary skill in chemical engineering.
A material acting as a cocatalys~ (or promoter) may optionally be added to a monomer feedstock before that feed is introduced to a reactor or it may be added separately to the reactor, e.g., to the catalyst bed. A variety of conventional cocatalysts or equivalents can be used including H20, hydrogen halides, R~H and RX wherein X = halides and R=C2-C24 secondary or tertiary alkyl and the likè. For example, gaseous, `anhydrous HCl, may bé employed as a SUBSrITUTE SHEET

W093J00373 PCT/US92/ ~ 54 . . . , , ~
21û~84~:

, cocatalyst. The KCl will be employed in a catalytically effective amount, which amount will generally range from about 50 to 5,000 ppm by weight of the monomer feed, preferably 50 to 500 ppm (e.g., 70 to 200 ppm) by weight of the monomer feed when the monomer feed comprises >S wt.% isobutylene, and preferably from about lOQ-5,000 ppm (e.g., 400-3,000 pp~) by weight when the feed comprises n-butenes and <S wt.%
isobutylene. If anhydrous HCl is added to the feedstream containing isobutene, t-butyl chloride is formed before contact with the solid catalyst. This has been found to promote the polymerization of the isobutene. Water, in a catalytic amount, may be added to the feedstock but is not preferred since it has a tendency to cause physical deterioration of the catalyst with time. Alcohols, such as the preferred lower alkanols (e.g., methanol), may also be added. As has been pointed out above, the monomer feed is preferably anhydrous, and the reaction mixture is also preferably substantially anhydrous (that is, typically contains <50 ppm, mor~ typically <30 ppm, and most preferably <10 ppm, by weight water based on the monomer feed).
The characteristics of the polymeric product of the present process will be dependent upon the monomer feedstream, the particular immobilized catalyst, the optional cocatalysts, and the reaction conditions. Typically, Mn of the polymeric product will range from about 300 to about 1,000,000, preferably 300 to about Soo,000, more preferably about S00 to about 100,000, and most preferably about S00 to about 25,000 gm/mole. The molecular weight distribution t~w/~n) will typically range from about 1.1 to about 8.0, more typically about 1.8 to about 3.0, and preferably about 1.8 to about 2.5. The molecular weight of the polymer produced according to the process of the SUBSTITUTE SHEET

W093/00373 PCT/US92/054~
2~ 8~

present invention is inversely proportional to the reaction temperature, and, surprisingly and unexpectedly, a relatively high molecular weight polymer can be produced at or near room temperature. In addition, all molecular weights of polymers can usually be produced at relatively lower temperatures by using the immobilized catalysts of the present invention when compared with conventional car~ocationic catalysts.
The product mixture may be withdrawn from the reactor and subsequently treated (e.~., by depressuring into a suitable gas/liquid separation drum or other vessel) for separation of gaseous components therefrom (e.g., unreacted monomer such as isobutene, butene, butane, and isobutane). If desired, these separated gases can be compressed, cooled and recycled to the feed inlet to the tubular reactor, although the need for such recycling is minimized or avoided by use of the process of this invention in view of the high olefin conversions which are obtainable. A portion of the liquid reactor effluent can be recycled to the feed to dilute the content of the monomers in the feed to the reactor, if necessary. Preferably, the monomers fed to the tubular reactor are substantially free of monomers recycled from the- tubular reactor effluent.
Therefore, the monomer feedstream is preferably contacted with the catalyst in the process of this invention on a once-throu~h basis.
In addition to polymerization processes, the immobilized catalysts of the present invention may also be used in alkylation processes. As is known in this art, alkylation may be simply c 3cribed as the addition or insertion of an alkyl group into a substrate molecule. Of particular interest is the alkylation of aromatic, hydroxy aromatic, olefin, alkyl halide and alkane substrates and mixtures thereof. The hydroxy aromatic and aromatic compounds include, but are not SUBSTITUTE SHEET

W093J00373 PCT/USg2/0 , . `, , ~ .
~ 8~;~ 48 -limited to, toluene, xylene, benzene and phenol.
Suitable alkylating agents include olefin, alkane, alkyl halide and mixtures thereof~ The composition of each class of alkylating agent is as described in conjunction with the corresponding substrate class of compounds subject to the proviso that the alkylating agent class be different from the substrate class employed.
The hydroxy aromatic substrate compounds useful in the preparation of the alkylated materials of this invention include those compounds having the formula:
~ r-(OH)z wherein Ar represents . ~a -(~)w and z is an integer from 1 to 2, w is an integer from 1-3, a is 1 or 2 and Ra = C1-C24 alkyl-Illustrative of such Ar groups are phenylene,biphenylene, naphthalene and the like. `-- The aromatic substrate compounds useful in the preparation of the alkylated materials of this invention include those compourids having the formulas:

.. Ar - Ra and (Ar ~ Ra)w SUBSTITUTE SHEET

W093~0373 P~T/VS92/~
21~39~5 _ 49 wherein R is H or Cl-C24 alkyl and wherein Ar represents:

~(~)w ; ~

~ or wherein a is one or two and wherein R = Cl-c24 alky~, C3 C24 cyclic, C6-C18 aryl, C7-C30 alkylaryl, OH, or H
and w = 1-3.
Illustrative of such Ar groups are benzene, phenylene, biphenylene, naphthalene, and anthrocene.
The alkane substrate which can be alkylated using the processes of the present invention include those having the formula CnH2n+2 including but not limited to butane, ethane, propane, methane, hepane, heptane, octane, nonane, decane and the like.
The alkyl halide substrate will typically have the formula R8Xr wherein R8 = Cl-C24 alkyl, C3-C24 cyclic, C6-C18 aryl, or C7-C30 alkylaryl and X = halide includin~ Cl, F, Br and I, and r i5 a number from 0 to 4. Examples of alkyl halides ~nclude t-butyl chloride, ethyl c~ ~ride, n-butyl chloride and l-chlorohexane.
The olefin substrate useful in the preparation of the alkylated materials of this invention, and which may also be alkylated, are known in the art and include those compounds having 2 to 200 carbon atoms. The olefins may be monomers, oli~omers or copolymers or polymers including copolymers.

SUBSTITUTE SHEET

W093/~373 PCT/US92/o~ ~

~ 1 0 9 '~
-- so --Nonlimiting examples which are illustrative of such compounds include ethylene, propylene, butene, C2-C24 mono or diolefin, polybutene, poly-n-butene, polypropylene, low molecular weight polyethylene, ethylene alpha-olefin copolymers, and combinations thereof and oligomers derived from C2-C24 olefins.
The selected olefins, alkanes, alkyl halides, aromatic or hydroxy aromatic compound are contacted with a suitable alkylating agent in the presence of a~
catalytically effective amount of at least one acidic al~ylation catalyst under conditions effective to alkylate the substrate selected. The alkylation catalyst comprises the immobilized catalysts of the present invention. Also useful as catalysts are preformed complexes (or complexes formed in situ) of the immobilized catalyst with aromatics such as benzene, toluene and the like.
The substrate and alkylating agent will generally be contacted under reaction conditions, including mole ratio, temperature, time and catalyst ratio sufficient to alkylate the substrate. The substrate will be generally contacted in a molar ratio of from about 0.1 to 10, preferably from about 1 to 7, more preferably from about 2 to 5, moles of the substrate per ~mole of ; the alkylating agent.
Conventional ratios of alkylating agent will typically be used. The ratio will typically be about 0.5 to 2:1, more typically about 0.8 to about 1.5:1, and preferably about 0.9 to about 1.2:1. The selected catalyst can be employed in widely varying concentrations. Generally, the catalyst will be charged to provide at least about 0.001, preferably from about 0.01 to 0.5, more preferably from about 0.1 to 0.3, moles of catalyst per mole of substrate charged to the alkylation reaction zone. Use of greater than 1 mole of the catalyst per mole of substrate is not generally required. The SUBSrITUTE SHEET

W093~373 PCT/US92~054~
2 ~ S

reactants can be contacted with the immobilized catalyst employing any conventional solid-liquid contacting techniques, such as by passing the reactants through the resin (e.g., in a catalyst bed or through the resin (e.g., in a catalyst bed or through a membrane impregnated or otherwise containing the catalyst or t~rough a conduit having deposited thereon a coating or layer of the catalyst) and the upper limit on the moles of catalyst employed per mole of substrate' compound is not critical.
The temperature for alkylation can also vary widely, and will typically range from about 20 to ~50C, preferably from about 30 to 150C, more preferably from about 50 to 80C.
The alkyl~tion reaction time can vary and will generally be from about 1 to 5 hours, although longer or shorter times can also be employed. The alkylation process can be practiced in a batchwise, continuous or semicontinuous manner.
Alkylation processes of the above types are known and are described, for example, in U.S. Patents 3,539,633 and 3,649,~29, the disclosures of which are -~hereby incorporated by reference.
Generally, the ~ conversions obtained in the alkylation according to the present invention will be greàter than about 50%, e.g., from 70 to 98%, and preferably from 80 to 95%~ based on the percentage of the alkylating agent charged which reacts. The precise conversion obtained will depend on the Mn of the substrate, e.g., polyalkene, the alkylation temperature, reaction time and other factors, and conversions will generally decrease somewhat as polyalkene ~n increases. The alkylation process of this invention is particularly beneficial for ole~ins having ~n of from about 300 to 5,000, preferably 300 to 3,000.

SUBSTITUTE SHEET

W093/~373 PCr~USg2/05454 211)984~

It will be understood that when the alkylating agent is a polyalkene it can be charged to the alkylation reaction zone alone or together with (e.g., in admixture with) other polyalkenes alkylating agents derived from alkenes having from 1 to 20 carbon atoms (butene, pentene, octene, decene, dodecene, tetradodecene and the like) and homopolymers of C3 to Clo, e.g., C2 to C5, monoolefins, and copolymers of C2 to C10, e.g., C2 to C5, monoolefins, said additional polymer having a number average molecular weight of at least about 900, and a molecular weight distribution of less than about 4.0, prefera~ly less than about 3.0 (e.g., from 1.2 to 2.8). Preferably such additional olefin polymers comprise a major molar amount of C2 to Cl0, e.g., C2 to C~ monoolefin. Such olefins include ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene, etc. Exemplary of the additionally charged homopolymers are polypropylene, polyisobutylene, and poly-n-~utene the like as well as interpolymers of two or more of such olefins such as copolymers of:~ ethylene and propylene; butylene and isobutylene; propylene and isobutylene; etc. Other copolymers include those in which a minor molar amount of the copolymer monomers, e.g., 1 to 10 mole ~, is a C4 to C18 non-conjugated diolefin, e.g., a copolymer of isobutylene and butadiene: or a copolymer of ethylene, propylene and 1,4-hexadiene; etc. The additional such olefin polymers charged to the alkylation reaction will usually have number average molecular weights of at least about 900, more generally within the range of about 1,200 and about 5,000, more usually between about 1,S00 and about 4,000. Particularly useful such additional olefin alkylating agent polymers have number average molecular weights within the range of about 1,500 and about 3,000 with approximately one double bond per chain. An especially useful additional such SUBSTITUTE SHEET

WOg3/~373 2 1 0 ~ g ~ ~ PCT/US92/0~4~

.
polymer is polyiso~utylene. Preferred are mixtures of such polyisobutylene with ethylene-propylene copolymers wherein at least 30 wt.% of the copolymer chains contain terminal ethenylene monounsaturation as described above.
The number average molecular weight for such polymers can be determined by several known techniques.
A convenient method for such determination is by gel permeation chromatography (GPC) which additionally provides molecular ,weight distribution information;
see W. W. Yau, J. J. ~irkland and D. D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, lg79.
As previously mentioned, the immobilized catalysts and processes of the present invention offer a number of advantages over conventional carbocationic catalysts and polymerization processes.
A particularly significant advantage of the immobilized catalyst and process of the present invention is that the catalyst is usable for prolonged periods of time before regeneration is required resulting in significant C08t savings, as well as the elimination of significant amounts of hazardous waste typically generatéd in conventional Lewis Acid processes. -Another surprising and unexpected advantageof the~present invention is that the polymerization process can be operated, depending upon the desired molecular weight of the polymer, at relatively higher temperatures, even ambient temperatures.
Yet another surprising and unexpected advantage of the present invention is that gaseous catalysts such as 8F3 can now be immobilized.

. . .

. , SUBSTITUTE SHEET

W093/00373 PCT/US92/~
~ .; . . .

21~98~5 - 54 ~

Another advantage of the immobilized catalysts of the present invention is that the catalysts are easy to dispose of in an environmentally advantageous manner.
Yet still another advantage of the immobilized catalysts of the present invention is that the catalysts can be regenerated in situ, for example, by first using an acid wash followed by Lewis Acid reagent.
Another advantage of the immobilized Lewis Acid catalysts of the present invention is that they can be used in most organic solvents. The immobilized catalysts do not require that their use be limited to specific solvents, for example, halogenated solvents.
And yet another advantage of the immobilized Lewis Acid catalysts of the present invention is that the polymers produced using these catalysts have little or no catalyst residue.
Polybutenes and other polymers and copolymers in the molecular weight range of 500 to 20,000 prepared in accordance with the process of the present invention are particularly useful as a feedstock for the production of improved lubricating oil dispersants.
These dispersants generally comprise the reaction product of polybutenyl (Mn of 700 to 10,000) succinic anhydride, or the acid form thereof, with monoamines or polyamines having at least one primary or secondary amino group such as the alkylene polyamines, particularly the ethylene polyamines, the polyoxyalkylene amines, aromatic and cycloaliphatic amines, hydroxyamines, monoaliphatic and dialiphatic substituted amines. Useful dispersants are also formed by reacting monohydric and polyhydric alcohols with the polyisobutenyl succini~ anhydride or diacid provided in accordance with this invention and preferred materials are thus derived from polyols having 2 to 6 OH groups SUBSTITUTE SHEET

W093/00373 2 1 ~ ~ 8 ~ ~ PCT/US92/054~

oontaining up to about 20 carbon atoms such as the alkene polyols and alkylene glycols. Also suitable are the polyoxyalkylene alcohols such as polyoxyethylene alcohols and polyoxypropylene alcohols, monohydric and polyhydric phenols and naphthols, ether alcohols and amino alcohols and the like. Borated derivatives of the foregoing dispersants are also useful, especially borated nitrogen containing dispersants resulting from boration with boron oxide, boron halide, boron acids ' and esters to provide 0.2 to 2.0 weight percent boron in the dispersant. Metals and metal-containing compounds can also form useful dispersants and these are compounds capable of forming salts with the polybutenyl succinic anhydride or acid (using the polybutenes of the present invention) These include metals such as the alkali metals, alkaline-earth metals, zinc, cadmium, lead, cobalt, nickel, copper, molybdenum, in the form of oxides, carboxylates, halides, phosphates, sulfates, carbonates, hydroxides and the like.
Lubricating oil compositions will usually contain dispersants in amounts of from about 1 to lS
weight percent based on the overall weight of the composition. Lubricating oil compositions will typically contain other additives in customary amounts to provide their normal attendant functions such as metal detergents or basic metal detergents, antiwear add~tives, antioxidants, viscosity modifiers and the like. Dispersants are conventionally packaged and dispensed in the form of solution concentrates containing about 20 to 50 wt.% dispersant in a mineral oil.
The following examples are illustrative of the principles and practice of this invention, although not limited thereto. Parts and percentages where used are parts and percentages by weight. The structure of SUE~STITUTE SHEET

W093~00373 PCT/US92~0 :: .
2~0~84~ -the catalysts where used in the examples are only meant to serve to identify the particular immobilized catalyst and do not repr~sent the actual structure of the catalyst.

,Example 1 (a) Co~olymerization of Pro~ylene and Hexenyl-9-BBN
Into a 500 ml evacuated flask containing 200 ml of toluene, 4 ml of propylene (50 mmol) was' introduced at a temperature of -78C. The flask was sealed and gradually warmed to room temperature to dissolve the gas. In a dry box, 4 g (20 mmol) of hexenyl-9BBN were added followed by a suspension of 0.168 g (1.113 mmol) TiC13AA ("AA" is alumina activated) and 0.754 g (6.604 mmol) Al(Et)3 aged for 1/2 hour in 30 ml sf toluene. Almost immediately, a precipitate could be seen in ~he deep purple suspension. The reaction was terminated after 112 hour by addition of isopropanol. A white, rubbery polymer was precipitated and then repeate,dly washed with more isopropanol. The white rubbery polymer was squeeze dried and then further dried in a vacuum cham~er to yield 3.5 g of borane-containing polypropylene.

(b) Synthesis of Po ~f~er~pylene-co-l-hexenyl-6-ol) 0.674 g of the borane-containing polypropylene copolymer of Part (a) was placed in 75 ml of THF in a 250 ml stirred roundbottom flask fitted with an airtight septum to form a cloudy white suspension. The stirred suspension was cooled to OC in an ice bath before the addition via syringe of 2 molar equivalents (based on alkylborane content) of degassed NAOH
solution followed by dropwise addition of 3 equivalents of 30% H22 solution. The flask was gradually warmed to 55C and held at that temperature for 4 hours. The . , SUBSTITUTE SHEET

W093/00373 PCT~US92/0~4~
2 ~ 5 functionalized copolymer was precipitated with water, washed with acetone, refluxed in MeOH (methanol), and again precipitated with water and washed with acetone.

Example 2 (a) Preparation of Immobilized Catalysts In a dry 200 ml flask, equipped with a magnetic stirring bar and a connecting tube leading to a nitrogen source, the functionalized copolymer (2g) of Example 1 was suspended in 50 ml of CH2C12 with 180 mg of triethyl aluminum (AlEt3) for 2 hours at ambient temperature. The composition of the copolymer included 98 mole % of propylene and 2 mole % of hexenol. The melting point of this polymer was about 165C. The solid particles were separated from solution by syringing out the liquid portion and then were washed with dry and oxygen-free CH2C12 several times. The resulting immobilized catalyst (PP-O-AlEt2) was dried for 24 hours, at room temperature and 10 ~m Hg pressure, before transferring into a dry box. For convenience, the following short hand designation of PP-0-AlEt2 is used with PP being the unfunctionalized polymeric units, i.e. polypropylene, -and -O-AlEt2 indicating- the immobilized catalyst structure, i.e.
-1-hexenyl-6-0-diethyl aluminum.

(b) Polymerization of Isobutylene A polymerization was carried out in a high vacuum apparatus consisting of two 200 ml flasks equipped with magnetic stirrers ~Figure 7). One stopcock 30 was used to separate two flasks (A and B) , the other stopcock 4 n located on the top of flask A was used to control the vacuum condition and inert gas flow. After the apparatus was dried for over 12 hours, a portion of the immobilized catalyst PP-OAlEt2 ~O.2 g) of part (a) was charged to flask B in a dry box SUBSTITUTE SHEET

W093/00373 PCT/US92/0~4~
~ 7 ~
Z1~8~5 condition. The system was connected to a vacuum line and pumped to high vacuum, and then 50 ml dry CH2C12 and 2 ml (1.2 g) dry isobutene were vacuum-distilled into flask A by immersing the flask in a dry ice/acetone bath. The catalyst to monomer molar ratio was 1/200. After controlling both flasks at 0C, the monomer solution in flask A was poured into flask B.
The polymerization occurred at ooc with stirring. After a half hour reaction time, the catalyst was allowed to settle. The solution portion, polyisobutylene, CH2C12 and unreacted isobutene, was then carefully poured back into flask A without disturbing the precipitate (immobilized catalyst). The precipitate was further washed by low temperature distillation of pure CH2C12 from flask A. This procedure was repeated several times to ensure complete removal of polyisobutylene from the surface of the immobilized catalyst. The product was then decanted from flask A. Evaporation under vacuum gave 1.2 g (100% yield) of viscous polymer. A GPC study of resulting poly~er showed a rela~ively high molecular weight (Mn = 24,516 and Mw = 160,062).
A repeat polymerization using the recovered catalyst and the same reaction condition gave about 1.05 g (87% yield) polyisobutylene. The polymer had slightly lower average molecular weight (Mn 14,325 and Mw = 120,111). A third cycle polymerization resulted in polymer with about 70% yield and similar number a~erage molecular weight, weight average molecular weight and molecular weight distribution.

Example 3 The immobilized catalyst of Example 2 (a) was used to polymerize isobuten~ in hexane solvent. The polynerization was carried out using the reaction procedure of Example 2 (b), using 0.2 g of PP-0-AlEt2 and 1.2 g of isobutene in 50 ml of dry hexane. The SUBSTITUTE SHEET

W093/00373 PCT/US92/054~
.~
21 ~8~

.
polymerization temperature was at OOC. The product was a water white, very viscous polymer with almost 100%
yield and moderate molecular weight (Mn 5,667 and =
22,496). This immobilized catalyst was reused for a Mw second batch polymerization to generate an 80%
yield with a reproducible molecular weight (Mn 6,330 and Rw c 21,898).

Exam~le 4 Following the procedure of Example 2 (a), hydroxy functionalized polypropylene copolymer (i.e.
poly(propylene-co-l-liexenyl-6-ol)) was reacted with excess AlC13 in CH2C12 solution. Due to the limited solubility of AlC13, the contact time was about 24 hours at r~om temperature. This reaction evolved HC1 and produced PP-o-AlC12 catalyst which was then washed free of unreacted AlC13 and HCl before drying under vacuum overnight, where PP-O-AlC12 is analogous to the short hand as described in Example 2(a).
This catalyst was used in the polymerization of isobutene using the procedure of Example 2(b). The solvent was CH2C12 and the reaction temperature was 30C. Within one half hour polymerization time, almost 100% yield of polyisobutylene was obtained with a very broad molecular weight distribution (~n 15,334 and =
369,495). The second cycle was operated at 0C. The yield was reduced to 55~ with a similar broad molecular weight distribution and a relatively lower molecular weight (Mn = 4,657 and Mw = 130,843).

ExamDle 5 Hydroxy group functionalized polypropylene copolymer (poly(propylene-co-l-hexenyl-6-ol)) (O.2g) suspended in 100 ml of CH2Cl~ solution was con~acted with BF3 by condensing BF3 (excess) into the solution.
The reaction mixture was stirred for 6 hours before SUBSrITUTE SHEET

W093/00373 PCT/US92/~

21~84~ - 60 -pumpin~ out the unreacted BF3, HF and CH2C12 solvent.
Under high vacuum (<5 um) for overnight, the catalyst was contacted with monom~r solution tl- 2 g of isobutene in 50 ml of hexane) using the technique of Example 2 (b) A viscous polymer was obtained with an overall yield of about 75%.

Examples 6-15 Cationic polymerizations were carried out in accordance with the procedure of Example 2(b) however, the i~mobilized catalyst used was PP-0-AlEtCl.
This was derived from the Lewis Acid aluminum ethyl dichloride (AlEtC12). PDI is the polydispersity index which is Mw/~n. This is the same as molecular weight distribution. A narrow molecular weight distribution, i.e. , low PDI, is desirable for use of the polymer as a dispersion agent. The results are presented in the following table.

Solvent Temp Time Mn PDI Yield `3 ( C) (I~) (%) Ex. 6hexane -10 2 9,500 2.7 35 Ex. 7hexane -10 4 10,200 3.1 55 Ex. 8hexane 0 4 4,050 3.9 65 Ex. 9hexane 0 6 4,700 3.2 80 Ex. 10hexane 25 4 2,100 3.7 70 Ex. 11hexane 25 6 1,750 3.8 90 Ex. 12hexane 25 8 1,850 3.6 100 Ex. 13CH2C12 0 2 15,300 3.4 65 Ex. 14CH2C12 0 4 14,700 3.1 85 Ex. 15CH2C12 0 6 13,500 2.8 95 SUBSTITUTE SHEET

W093/00373 PCT/US92/0~ ~
. . .
2 1 ~ S

Examples 16-21 (a) Preparation of Supported Catalysts ps-o-AlcL2 In the following Examples, the supporting material was hydroxy functionalized polybutene-l copolymer ~poly(butene-l-co-l-hexenyl-6-ol)) which contained 10 mole % of 1-hexenyl-6-ol (hydroxyl groups). The pol~mer was ground to a fine powder form having high surface area ~y freezing with liquid nitrogen and then pulverizing by placing in a ~eal~d metal container with a metal ball and shaking the container and its contents for a sufficient length of time to pulverize the immobilized catalyst such that the average particle size was about O.1 mm and the particles ranged in size from about 0.01 mm to about O.5 mm. In a dry 200 ml flask, the hydroxyl functionalized polybutene copolymer (O.2 g) was suspended in 50 ml of toluene solution with 10 mole %
excess ethyl aluminum dichloride (EtAlC12) for 5 hours at 25C. The powders were separated from solution by filtration through glass fret, and then were washed with dry and oxygen-free toluene for several times.
After drying, the resulting immobilized catalyst tPB-O-AlC12) was subjected to the structural characterization. Elementary analysis and 23Al NMR conf irmed the complete conversion of -OH to -OAlCl2 groups.

(b) Polymerization of Isobutylene A polymerization of isobutylene by PB-O-AlCl2 was carried out in a high vacuum apparatus as described in Example 2. PB-O-AlC12 (50 mg) was charged to flask B
in a dry box condition. The system was connected to a vacuum line and pumped to high vacuum, 50 ml dry hexane and 4 ml (2.4 g) dry isobu~ylene were vacuum-distilled into flask A by immersing the flask in a dry ice/aceton bath. The monomer solution in flask A was warmed up to room tempera~ure before pouring into flask B. The SUBSl ITUTE SHEET

W093/~373 PCT/US92/ ~ ~
'~109~31~,, . `'"' ' polymerization occurred at ambient temperature with stirring. After 20 minutes reaction time, the catalyst was allowed to settle. The solution portion, polyisobutylene/hexane, was then carefully pipetted our from flask 8 without disturbing the precipitate (immobilized catalyst). After solvent-evaporation under vacuum, a viscous polyisobutylene polymer was obtained.
This procedure was repeated for several times to evaluate the polymerization reactivity in the subsequent cycles. The results are summarized in the following Table 2.

Reaction Temp.
Time (Min.~ Yield (oC) Mn PDI
Ex. 16 20 100% 25 1067 2.02 Ex. 17 20 100% 25 1157 1.61 Ex. 18 20 100% 25 1135 1.75 Ex. 19 10 100% 25 1120 1.68 Ex. 20 40 100% 0 4228 2.37 Ex. 21 30 100% 0 4526 2.34 PDI = Polydispersity Index = Mw Mn :

Examples 22-31 Polymerization of Isobutvlene bv Immobilized Catalysts P~-O-AlC12 As in Exanples 16-21, the same functionalized polybutene-l copolymer with 10 mole % of 1-hexenyl-6-ol (hydroxyl groups) was used in the preparation of polyisobutylene. The major difference was the form of functionalized polymer. A piece of hydroxylated polybutene solid (0.1 g) was reacted with EtAlC2 overnight at 25C. The~reaction was complete despite SUBSTITUTE SHEET

WOg3/00373 PCT/US92/~
2~89L~

the inhomogeneity of reaction conditions. Elementary analysis showed the Ratio of Al:O:Cl equal to 1:1:2.
This indicated that the reaction was occurring at the ethyl site. The polymerization of isobutylene by P~-O-AlC12 particles was carried out in a high vacuum apparatus as described before. In each reaction cycle, 4 ml (2.4 9) of dry isobutylene were used. The results are summarized in Table 3, with RT at about 25C.

Catal~st Solvent Tem~ ~ Yield Mn PDI
(hr) (%) Ex. 22 P~-0-AlC12 Hexane RT 2 lOo 1,37S 3.03 Ex. 23 PB-0-AlC12 Hexane RT 20 100 1,964 2.59 Ex. 24 PB-O-AlC12 Hexane RT 20 100 1,316 2.41 Ex. 25 PB-0-AlC12 Hexane RT 5 100 1,014 2.15 Ex. 26 PB-O-AlC12 Hexane RT 3 90 1,398 2.38 Ex. 27 PB-0-AlC12 Hexane RT 1 45 1,237 2.36 Ex. 28 PB-0-AlC12 Hexane RT 5 100 1,125 2.41 .. . .
Ex. 29 PB-O-AlC12 Hexane 0C 6 70 5,454 2.63 Ex. 30 PB-O-AlC12 CH2C12 -30C 1 100 180,976 4.12 Ex. 31 PB-0-AlC12 CH2C12 0C 1 95 100,253 8.6 Exam~les 32-34 PolYmerization of Isobutvlene A piece of hydroxylated polybutene-l copolymer solid (0.1 g) as in Examples 16-21 (i.e.
poly(butene-l-col-hexenyl-6-ol)) was reacted with BF3 which was condensed in CH2C12 solution. The reaction took place for 2 hours at 25C before distillating out SUBSrlTUTE SHEET

O 93/00373 PCl /US92/05454 r~
2~S84~ 64~

excess BF3 and CH2C12The resulting L~mobilized catalyst was used in the polymerization of isobutylene. Similar reaction procedures were followed in the evaluation of the i D obilized catalyst. The results are summarized in the following Table 4. The reaction of the BF3 with the hydroxylated polybutene-1 copolymer resulted in the formation of a complex wherein the BF3 is complexed with the hydroxyl groups in the copolymer via a pi (~) bond.

Catalyst Solvent Temp Time Yield Mn PDI
(hr) (%) EX. 32 PB-OH-BF3 Hexane RT 5 95 400 1.1 EX. 33 P8-OH-BF3 Hexane RT 12 98 445 1.2 EX. 34 PB-OH-BF3 Hexane 0C 4 9 576 1. 2 EX. 3S PB-OH-BF3 Hexane -15C 4 50 662 1.72 Examples 36-46 Polymerization of Isobuty~ene by~a Mixture_of PB-O-AlEtCl and (PB-0)2-AlCl A piece of the hydroxylated polybutene-l copolymer solid (O.1 g) of Examples 17-22 was reacted with Et2AlCl overnight at 2SC. The reaction was complete, resulting in a mixture of PB-O-AlEtCl and tPB-0)2-AlCl. This mixed, solid particle, immobilized catalyst was used in the polymerization of isobutylene.
The reaction conditions of Examples 16-21 were used to evaluate the reactivity of the immobilized catalyst.
The reaction time was about 5 hours. The results are summarized in the following Table 5.
.

SUBSTITUTE SHEET

W093/00373 PCT/US92/ ~ ~
2~098~

Temp. Yield Solvent (C) MnMw ( % . ) Ex. 36 Hexane -10 9,525 25,254 100 Ex. 37 Hexane 0 4,037 16,267 95 Ex. 38 Hexane 0 4,705 15,454 90 Ex. 39 Hexane 25 2,103 7,803 ~5 Ex- 40 Hexane 25 2,038 7,408 82 Ex. 41 Hexane 25 1,740 6,540 100 Ex. 42 Hexane 25 1,844 6,763 100 Ex. 43 CH2C12 0 24,516 90,064 100 Ex. 44 CH2Cl2 0 12,575 100,235 >80 Ex. 45 CH2Cl2 -30 45,334 180,976 lOo Ex. 46 CH2Cl2 0 8,94~ 100,253 95 E~ample 47 The immobilized catalyst of Examples 6-15 is used to make a coating composition. The coating composition is made by mixing S wt.~ parts of the catalyst with 95 wt.~ trichlorobenzen~ in a conventional mixing vessel at room temperature for a sufficient amount of time to completely dissolve ~he immobilized catalyst.
The composition is coated onto the interior surface of a 316-stainless steel reactor vessel. The coating is applied using a conventional spraying apparatus. After application, the coating is dried by heating at l50~C under vacuum until dry. The coating is uniform and has an average thic~ness of about .1 mm.
The coated reactor may be used in a polymerization process to polymerize monomer feeds.

Exam~le 48 The immobilized catalyst of Examples 6-15 is fed to a conventional injection molding apparatus SUBSTITUTE SHEET

W093/~373 PCT/US92/054~4 - 21(~9~

having a feed means, heating means, cooling means, extruding means and molds. The catalyst is heated under sufficient heat and pressure to a temperature of at least about 185C, injected into the mold and molded under sufficient heat and pressure, and for a sufficient time, to form an object having the shape of a column packing ring. The object is then cooled and removed from the mold. The object may be used in a packed column reactor vessel to polymerize monom~r feeds.

Example 49 The immobilized catalyst of Examples 6-15 is placed into a conventional vessel having a heating jacket and heated to a temperature of about 200C for a sufficient amount of time to liquify the immobilized catalyst. Ceramic spheres having a diameter of about 1 mm are dipped into the liquid immobilized catalyst and removed. The spheres have a liquid coating of the immobilized catalyst which solidifies upon cooling. The coated spheres are used as catalyst in a batch reactor in a polymerization process.
.
Example 50 The immobilized BF3 of Examples 33-36 is charged to a conventional stirred tank reactor having heating and cooling means and agitating means. An excess molar ratio of an aromatic hydrocarbon (benzene) is charged to the reactor. A polyalkene (poly-n-butene (PNB)) is fed to the reactor. The PNB reacts with the benzene under suitable reaction conditions at a sufficient temperature (40C) and pressure, and for a suf f icient time, effective to alkylate the aromatic hydrocarbon. The resulting product PNB alkylated benzene, is then discharged from the reactor and separàted from unreacted benzene by distillation.

SUBSrlTUTE SHEET

~W093/00373 2 ~ ~ 9 ~ ~ ~ PCT/US92/054~

ExamDle 51 The process of Example 50 is repeated except that the immobilized catalyst is the immobilized catalyst of Example 22-31. The aromatic hydrocarbon is benzene and the alkylating olefin is propylene oligomer with an average molecular weight of about 3i40. The reaction temperature is about 300C and the reactor is a continuous stirred tank reactor.

Exam~le 52 A continuous tubular reactor is packed with the immobilized catalyst of Examples 16-21. Isobutane is fed into the reactor in a feedstream and, simultaneously, isobutylene from a refinery feedstream is fed into the reactor. A cocatalyst, HCl, is also fed into the reactor. The mixture is held in the reactor for a sufficient length of time and under sufficient temperature and pressure to alkylate the butane to a degree of about SO%. Branched octane (alkylated butane) and the unreacted monomers are withdrawn in a discharge stream. The branched octane is separated from the urireacted monomers by distillation.
, Exam~le 53 The functionalized copolymer of Examples 16-21 is reacted with n-butyl lithium to form an intermediate salt in the following manner. To a conventional reactor vessel having a mixing means, is charged hexane and the functionalized copolymer of Example 1. The functionalized copolymer is dispersed in the hexane by mixing. Then, an excess (1.1-5 times molar ratio) of n-butyl lithium hexane solution (1.5 m) is added to the vessel. The reaction is held at room temperature (about 25C) for two hours. Then, the resulting intermediate (functionalized copolymer salt) SUBSrITUTE SHEET

W093/00373 PCT/US92/0~ ~

~iO~8~S - 68 -is removed by filtration and washing with pure hexane. , The resulting intermediate is then reacted with BF3 utilizing the procedure of Examples 32-35 to form a catalyst having a structure identified as PB-O-BF2 wherein the BF3 is chemically reacted with, and chemically bonded to, the functionalized thermoplastic copolymer. Similar reaction conditions are followed in the evaluation of the catalyst using isobutylene monomer as a feed. The resulting polymers are observed to have an Mn in the range of about 1,000 to about 1, 500.

Functionalization chemistry, as recited in Chung, T.C.; Macromolecules, 1988, 21, 865, Ramakrishnan, S.; Berluche, E.; Chung, T.C.;
Macromolecules, 1990, 23, 378, Chung, T.C.; ~hubright, D., Macromolecules, 1991, 24, 970, using a borane monomer as the comonomer in the polymerization of polyolefins by Ziegler-Natta catalyst, was used to prepare a polyolefin structure. Isotactic polypropylene, as recited in Chung, T.C.; Rhubright, D., Macromolecules, 1991, 24, 970, with 5 mole % of hydroxy groups and isotactic polybutene (PB-OH) with 12 mole % of hydroxy groups, were used as the substrates to immobilize Lewi~ acids which are active in the carbocationic polymerization of isobutylene. Both functionalized polyolefins have "brush-like"
microstructures, as recited in Ch~mg, T.C., Chem. Tech.
27, 496, 1991.
Figure 1 shows the PP-OH product having crystalline phase "5" and functional groups "A"

,. 21~984rj selected from -OH, -I, AIX2 and BX2 wherein x is a halide or alkylhalide. The structure of hydroxylated polypropylene f ollows:
CH3 CH3 C~3 C~3 C~3 C~3 CH3 -C~2-CEI-C~2-CII-C~2-C~-CH2-C~I-CE12-C~ -CE12-CR-C82-C~-CH2-CH-C82-CEI-Cli2-CE~-C~2 C~2 C~2 CH2 ~ CH2 CH2 I
C~2 CH2 C~, I l I
C~2 C~12 C~2 I
O O O

Several experiments were introduced in which the hydroxylated polyolefins, polypropylene or polybutene, were reacted with Lewis acids, such as EtAlCl2, Et2AlCl and BF3 according to the following equation:
, b x P-OH +-a-M > P-O-M
c ~ Y
(I) (II) P is the partially crystalline polyolefins which have 5 or 12 mole % of hydroxy groups. M is B or Al atom, the ligands (a, b,~c) can be either alkyl or halogen groups and x, y can be a, b, c or oxygen. The hydroxy groups react with either alkyl grou~ or halogen.
Additionally, two hydroxy groups can react with one M.
The reaction was usually carried out at room temperature by stirring the hydroxy~lated polymer with excess Lewis acid solution for a few hours. The unreacted reagent was removed by washing the resulting immobilizéd catalyst withipure solvent for several SUBSTITUTE SHEET

W093/00373 PCT/US92/0~ ~
.

~ ~ 70 -times. In general, the alkyl groups have been found to be more reactive to hydroxy group than halides. To enhance the reactivity in BF3 case, the hydroxy groups in polymer were usually metalated, such as by the reaction with alkyl lithium, before immobilization reaction.
Solid state 27Al and llB NMR measurements were used to analyze the catalytic species in the immobilized catalyst. Three immobilized catalysts were studied in detail, by comparing the immobilized catalysts with their corresponding soluble ones.
Figure 4 shows the 27Al NMR spectrum of the catalyst (A), prepared by reacting hydroxylated polypropylene with EtAlC12 at room temperature. Only a singlet peak at 89 ppm, co~responding to -OAlC12 with four coordinations, as recited in Benn, R.; Rufinska, A., Angew. Chem. Int. Ed. Engl., 1986, 25, 861, was observed with the absence of 170 ppm, corresponding to EtAlCl2. It was surprising to find such a selective reaction, the alkyl-aluminum bond is much more reactive than aluminum-halide bond in the reaction with alcohol.
The same chemical reaction was also observed in the reference sample, using l-pentanol, instead of the hydroxylated polypropylene, in the reaction of EtAlCl2 under the similar reaction condition. Figure 4A is the solution 27Al NMR spectrum of resulting C5-OAlCl2, which indicates the same chemical shift, corresponding to single -OAlCl2 species. The elemental analysis study, with the same theoretical and experimental mole ratio of elements in C5-OAlCl2 compound, also reconfirms the result.
The immobilization reaction was substantially complete in relatively mild reaction condition. Most of hydroxy groups disappeared despite the shape and size of hydroxylated polymer particles. The elemental analysis results show that the concentration of Al SUBSTITUTE SHEET

W093/00373 2 ~ PCT/USg2~054~
.

. . .

species in the immobilized catalyst was very close to that of hydroxy group in the original functionalized polyolefin. The complete reaction in this heterogeneous system supports the morphologic arrangement in Figure 1, most of hydroxy groups are located in the amorphous phase which can be easily reached by EtAlC12 reagent.
In the case of Et2AlCl, there are two alkyl groups which are very reactive to hydroxy group. Using excess Et2AlCl reagent to the hydroxy groups (12%) in PB-OH, it was expected that the resulting immobilized catalyst (B) would be a mixture. Figure 5 compares the solid state 27Al NMR spectrum of the immobilized catalyst (B) to the solution 27Al NMR spectrum of the corresponding small molecule by reacting l-pentanol with the stoichemetric amount of Et2AlCl (Figure 5A).
Both show similar results with three main peaks at about 93, 37, 4 ppm, corresponding to -OAlEtAl (four coordinations), -0)2AlEt (five coordinations) and -O)2AlCl (six coordinations) respectively, as recited in Benn, R.; Rufinska, A., Angew. Chem. Int. Ed. Engl., 1986, 25, 861, and no peak at 170 ppm, corresponding to Et2AlCl.
The relative peak intensity between three Al peaks was also very similar in both spectra. The same degree of the reaction to form various species seems to indicate that the availability of hydroxy groups in polybutene solid is very close to that of soluble 1-pentanol case. This result is also consistent to the morphologic structure of "Brush-like" hydroxylated polybutene (Figure 1 Catalyst (C) is an immobilized BF3 catalyst.
The raaction between BF3 and hydroxylated polymers (PB-OH) was conducted in two ways. The direct reaction between BF3 and hydroxy group is very slow, and possibly forms the 8F3/OH complexes. The more SUBSTITUTE SHEET

WO93/0D373 PCT/USg2/0~ ~
~Ç7~
2 1 ~

effective immobilization reaction was carried out by using alkoxide groups. The metallization reaction of hydroxy groups was done by simple mixing of the polymer particles with butyl lithium solution. After washing out the excess butyl lithium, the polymer particles were subjected to BF3/CH2Cl2 solution. The similar procedure was done in the control experiment, using 1-pentanol small molecule. Figures 6 and 6A compares tneir llB NMR spectra. Both spectra are almost identical with a peak at about 0 ppm, corresponding to -OBF2 group, as recited in Noth, H.; Wrackmeyer, B.;
Nuclear _Magnetic Resonance Spectroscopy of Boron Compounds; Springer-Verlag, 1978. This result was also reconfirmed by elemental analysis study, it shows the mole ratio of 1:2 between B and F elements in PB-OBF2 sample.

Materials and Measurements In Examples 54-57 the following chemicals, 9-borobicyclononane (9-BBN~, Al(Et)3, AlEtCl2, Al(Et)2Cl and BF3 (Aldrich), and TiCl3AA (Stauffer), were used as received. HPLC grade toluene and THF were distilled from sodium anthracide. Isopropanol and 1,5-hexadiene were dried with CaH2 and distilled under N2. Propylene (Matheson) was passed through P205 and NaOH columns before drying with Al(Et)3 at low temperature.
Isobutylene (Matheson) was used without further purification. All the manipulations were carried out in an innert a~mosphere glove box or on a Sclenck line.
The molecular weight of polyisobutylene was determined using Waters GPC. The columns used were of Phenomenex Phenogel of 104, 103, 500 and 100 A. A flow rate of 0.7 ml/min was used and the mobile phase was THF. Narrow molecular weight polystyrene samples were used as standards. All of the solution NMR's were done on Bruker AM 300 machine. In 27Al NMR studies, toluene SUBSTITUTE SHEET

W093/00373 PCT/US9~/0~ ~
" - .
2 1 ~

was used as solvent with deuterated toluene as lock solvent. For lH NMR studies, deuterated chloroform was used as solvent. MAS 27Al NMR were conducted at CSU
NMR Center on a Bruker AM 600 NMR spectrometer (27Al resonance frequency of 156.4 MHz and 14.5 KHz MAS
speed). MAS llB NMR were conducted on Chemagnetics CMX
300 NMR spectrometer (llB resonance frequency of 95.4 MHz and 4 KHz MAS speed).

Preparation of HYdroxylated Polyolefins In a typical case, 1.9 ml of propylene at approximately 78C (.0293 moles) was transferred into a 500ml evacuated flask containing 150ml of toluene. The flask was sealed and gradually warmed to room temperature to dissolve the gas. In a dry box; 11.987g (0.0587 mole) of hexenyl 9-BBN were added followed by a suspension of 0.168g (1.113 x 10 3) TiC13AA and 0.754g (6.604 x 10 3 mole) Al(Et)3 aged for 1/2 hour in 30ml of toluene. Almost immediately precipitate could be seen in the deep purple suspension. The reaction was terminated after 1/2 hour by addition of isopropanol.
The polymer was precipitated and then repeatedly washed with more isopropanol. Borane containing polypropylene (0.674g) was placed in 75ml of THF in a 250ml roundbottom fitted with an air-tight septum to form a cloudy white suspension. The stirring suspension was cooled to 0C in ice bath before the addition via syringe of 2 molar equivalents (based on alkylborane content) of degrassed NaOH solution followed by dropwise addition of 3 equivalents of 30% H22 solution. The flask was gradually warmed to 55C and held at that temperature for 4 hours. The polymer was precipitated with water, washed with acetone, refluxed in MeOH, and precipitated with water and again washed with acetone.

. .

SUBSTITUTE SHEET

84~

Immobilization of Aluminum Compounds (EtAlC12 and Et2AlCl) r ._ ..- '~~--Two hydroxylated polymers, polypropylene containing 5mole % hydroxy groups and polybutene containing 12 mole % hydroxy groups were used in the preparation of immo~ilized catalysts. ~oth polymers were slightly swellable in toluene. The reactions with the aluminum reagents were carried out at room temperature under the inert atmosphere.
Both fine powder and big chunk polyolefin particles were treated in the same way. In a typical example, the hydroxylated polyolefin (150 mg) polymer, suspended in toluene (15 ml), was mixed with excess aluminum compounds (approximately 10 mmole). After a reaction time for 3 hours, polyolefin was filtered and washed with hexane repeatedly to remove remaining aluminum compounds. Based on the elemental analysis and 27Al NNR studies, most of hydroxy groups were reacted without any unreacted aluminum compound in the polymer.

Synthesis of Cs-0-AlC12 In a control reaction, pentanol (0.5 ml, 4.6 mmole) dissolved in 5 ml toluene was reacted with 0.4B
ml (4.6 mmole) EtAlC12 which was diluted with 5 ml toluene. The solution of EtAlC12 was cooled to approximately 78C and to this cooled solution pentanol solution was added dropwise. It was stirred at approximately 78C for 15 minutes and then warmed up to room temperature. Toluene was removed under vacuum.

Immobilization of Boron Trifluoride In the reaction with BF3, polyolefin containing hydroxy groups (150 mg) was reacted with a saturated solution of dichloromethane (15 ml) with boron trifluoride for 12 hours. The excess boron trifluoride and dichloromethane was removed under SUBSTITUTE SHEET

W093/00373 PCT/US92/0~ ~
:~-` 2 ~

vacuum. The most effective method involved a pretreatment of hydroxylated polyolefin (150 mg) with O.1 ml (1 mmole) of n-BuLi (10 M) in 7 ml of toluene for 1 hours. Polyolefin was filtered and washed with hexane to remove excess lithium compounds. The traces of solvent from polyolefin powder were removed by vacuum. To this polymer a saturated solution of dichloromethane with BF3 was added. This mixture was stirred at room temperature for 3 hours.
Dichloromethane and excess BF3 were removed on vacuum line.

Synthesis of_C5-0-BF2 Pentanol, 0.2 ml (1.84 mmole) was dissolved in

5 ml dichloromethane. To this solution, 20 ml of saturated solution of dichloromethane with BF3 was added at room temperature. This mixture was stirred for 15 minutes. Dichloromethane and residual BF3 was removed under vacuum.

Poly~e~ization of Isobutylene The polymerization was carried out in a high vacuum apparatus as shown in Figure 7. The system consists of two 100 ml flasks (10 and 20) and one stopcock (30) was used to separate flasks. The other stopcock (40) was used to control the vacuum condition and nitrogen flow. In the dry box, the immobilized Lewis acid catalyst, such as 100 mg of catalyst (A), was charged to the flask A, the valve (40) was then closed. The whole apparatus was moved to a vacuum line and was pumped to high vacuum before closing the valve (40). Isobutylene (4 ml, 50 mmole) was condensed in the flask B and dissolved in about 20 ml hexane which was vacuum-distilled into the flask B. Isobutylene solution was warmed up to required temperature and transferred to the catalyst in flask A. After stirring SUBSTITUTE SHEET

W093/00373 PCT/US92~0~ ~
r~
2~8~i the reaction mixture for required time, PIB solution was separated from immobilized catalyst by filtration in the dry box condition. PIB was obtained by evaporating the solvent under vacuum. The immobilized catalyst was then recharged to the flask A and the entire process was repeated.

Example 54 -Polymerization of Isobutylene by Polyolefin Immobilized Catalysts The polymer immobilized catalyst was used as the Lewis acid catalyst (A) in the carbocationic polymerization of isobutylene as follows:
fH3 CH2=~

~M~
Y

2 ~ ] x After the polymerization reaction, polymer solution (PIB) was filtered out and catalyst was reused in the subsequent polymerization reactions. In other words, the recovered catalyst was contacted with another isobutylene/hexane solution again, then following the, same separation and recovery processes. The immobilized catalyst usually was recycled for a number of times without any eignificant reduction in its activity. Table 6 summarizes the results of PIB
prepared by the fine powder form (particle size < 1 mm) of catalyst (A), polypropylene bounded -OAlC12 catalyst.

SUBSTITUTE SHEET

W093/00373 P~T/U~92/05454 _ 77 21~ 5 Table 6 A Summary of PIB Prepared by_Fr~ _AlC12 ffine powder~

Run # Solvent Temp. Time Mn PDI Yield (Min) %
1 hexane RT 90 1,050 2.0 lOo 2 hexane RT 60 1,150 1.6 100 3 hexane RT 20 1,150 1.8 100 4 hexane RT 15 1,140 1.6 100 8 hexane RT 15 1,180 1.5 100 hexane 0C 15 4,540 2.57 100 * hexane RT 15 1,180 2.3 100 * hexane ooc 15 5,450 2.63 100 (* Control~ pentanol based C5-0-AlC12 catalyst) The monomer to catalyst ratio was about 500. In most reaction cycles, the qualitative conversion from monomer to polymer was completed within 15 minutes.
The same reactivîty can be maintained in subsequent reaction cycles. This high catalyst reactivity is ve~y unusual, especially in the heterogeneous reaction. The polymer-immobilize catalyst almost had thè same activity as the corresponding small molecule, C5-0-AlC12, which was used as the control experiment and was studied under the same reaction condition.

Example 55 Table 7 shows another result of PIB prepared by catalyst (A) with the same overall catalyst concentration. However, catalyst (A) had particle size > 5 mm, instead of the fine powder form. Th~
experimental results of many consecutive reaction cycles are shown in Table 7.

SUBSTITUTE SHEET

W093/00373 PCT/US92/0~ ~

21~38~5 - 78 -Table 7 A Summary of PIB Prepared by PP-O-AlC12 ¢chunk~
Run # Solvent Temp. Time Mn PDI Yield (Min) 1 hexane RT 3 1,370 3.03 100 2 hexane RT 2 1,660 2.59 100 3 hexane RT 1 1,230 2.36 65 4 hexane RT 3 1,110 2.56 lOo 8 hexane RT 2 1,400 2.38 92 14 hexane RT 3 1,320 2.57 100 hexane 0C S 5,450 2.63 76 In this case, the yield of PIB is very dependent on the reaction time. It required about three hours to complete the conversion. This slow carbocationic polymerization of isobutylene is believed to be due to the availability of catalyst. The big particles of PP-O-AlCl2 are believed to greatly reduce the surface area of catalyst. The number of the active sites on the surface was very small. Despite the difference in the reaction rate upon the particle size, the catalyst can be recovered and reused in the subsequent reaction cycles. Elemental analysis and 27Al NMR results show no significant change in the aluminum species after more than 10 reaction cycles.

Example 56 In general, the use of the other immobilized catalysts, such as catalyst (B) and (C) as recited a~ove, resulted in the same recycle and reuse of the catalysts as obtained in the isobutylene polymerization using catalyst (A). The same surface area-activity relationship was also observed. However, the resulting PI8 structures, in terms of molecular weight, molecular weight distribution and unsaturation, were quite different. As shown in Examples 36-42, catalyst (B) SUBSTITUTE SHEET

resulted in higher molecular weight PIB than catalyst (A), and the molecular weight distribution of PIB was usually very broad, even bimodal. This phenomenon may be related to the multiple reactive species, -OAlEtCl and -0~2AlEt, involved in the polymerization.
On the other hand, the catalyst (C), PB-O-BF2, produced, using the same process as Examples 36-42, relatively low molecular weight PIB with quite narrow molecular weight distribution as shown in Table 8.

Table 8 A Summary of PIB Prepared by PB-O-BF3 (powder) Run # Solvent Temp. Time Mn PDI Yield (Min) %
1 hexane RT 15 405 1.1 100 2 hexane RT 15 450 1.2 100 3 hexane RT 15 450 1.2 100 4 hexane RT 15 420 1.4 100 hexane 0C 15 580 1.2 100 8 hexane 0C 15 640 1.5 100 * hexane RT 5 500 1.9 100 * hexane 0C 5 1080 2.0 100 (* Control, using pentanol based C5-O-BF2 soluble catalyst) Moleçu~a~ Structure of PIB
Figures 2 and 2A show the lH NNR spectrum of PIB which was prepared by catalyst (A) (PP-O-AlC12) at room temperature. The overall spectrum is very similar to those of PIB prepared by soluble Al cataly~ts, such as AlC13, EtAlC12, Et2AlCl, and the controlling C5-O-AlC12 catalyst. Two major peaks are at 0.95 and 1.09 ppm, due to CH3 and CH2 protons in PIB polymer. There are some weak peaks located in the olefinic region, between 4.5 and 6.0 ppm.

SUBSTITUTE SHEET

W093/00373 PCT/US92/~
8 ~ 5 The unsaturated double bond in polymer chain is the evidence of proton chain transfer reaction during the polymerization. In conjunction with the GPC
molecular weight studies, the integrative intensity of olefinic region implies on average a double bond per polymer chain. In details, there are two quartets at 5.4 and 5.2 ppm and two singlets at 4.9 and 4.6 ppm.
The singlets at 4.9 and 4.6 ppm are indicative of two types of nonequivalent vinylidene hydrogens, as recited in 25, which may be located at the end of polymer chain. The quartets at 5.4 and 5.2 ppm are the olefinic hydrogens coupled to methyl ~roup, which are due to the internal double bonds, as recited in 26.
The lH NMR peak assignments are summarized in Table I
above.
A significantly high amount of internal double bonds with various structures are present, which indicates carbocationic isomerization taking place by Lewis acid catalyst after the polymerization reaction.

Reactive PIB
A different lH NMR spectra of PIB was observed by using immobilized catalyst C (PB-O-BF2) at 25 and 0C. As shown in ~igures 3 and 3A, the chemical shifts in double bond region consist of two major singlets at 4.9 and 4.6 ppm, corresponding to terminal double bond, and two small peaks at 5.15 ppm, corresponding to internal double bond.
Comparing the integrated intensities between olefinic peaks, shown in Figure 3A, the PIB prepared at 0C contains more than 85% of terminal double bonds.
Theoretically, the maximum percentage of terminal double bonds in the final PIB cannot be more than 75%.
It is reasonable to speculate that some effects from the substrate may play a role to control the termination reactions and to avoid any isomerization SUBSTITUTE SHEET

WOg3/~0373 2 1 0 9 ~ 4 S PCTJUS92/~

, reactions. The control experiment, using C5-o-BF2 soluble catalyst under the same reaction condition, resulted in more than 30 mole% of internal double bonds.
Although this invention has been shown and described with respect to the detailed embodiments thereof, it will be understood by those skilled in the art that various changes in form and detail thereof may be made without departing from the spirit and scope of the claimed invention.

SUBSTITUTE SHEET

Claims (57)

CLAIMS:

1. Immobilized Lewis Acid catalyst comprising polymer having at least one Lewis Acid immobilized within the structure therein, said polymer having monomer units represented by the structural formula:
--[A]a--[B]b--[C]c--wherein a represents 1 to 99 mole %
b represents 0 to 50 mole %
c represents 1 to 99 mole %
a + b + c = 100%;

A is B is C is selected from the group consisting of:

(I) ;

(II) ; and, (III) combinations thereof, wherein D is OH, halide, OR4, NH2, NHR3, OM', or OM'';
E is the residue of the reaction of at least one Lewis Acid with the D substituent of monomer unit B;
R1 represents proton, C1-C24 alkyl group, or C3-C24 cyclo-alkylene;
R2 represents C1-C24 alkylene group, C3-C24 cycloalkylene, C6-C18 arylene, or C7-C30 alkylarylene;
R3 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl;
R4 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl; and M' represents alkali metal; and M'' represents alkaline-earth metal.

2. A process of manufacturing a molded immobilized catalyst comprising heating a thermoplastic immobilized Lewis Acid catalyst of claim 1 to a sufficient temperature to produce a flowable state, transporting the heated, immobilized catalyst under sufficient pressure into a mold containing at least one cavity, filling said cavity with the immobilized catalyst, cooling the molded immobilized catalyst for a time sufficient to achieve a non-flowable state, and removing the molded catalyst from said mold.

3. A process for polymerizing cationically polymerizable monomer comprising contacting said monomer with a catalytically effective amount of an immobilized Lewis Acid catalyst in a manner and under conditions sufficient to polymerize said monomer, wherein said immobilized catalyst comprises polymer having at least one Lewis Acid immobilized within the structure therein, said polymer having monomer units represented by the structural formula:
--[A]a--[B]b--[C]c--wherein a represents 1 to 99 mole %
b represents 0 to 50 mole %
c represents 1 to 99 mole %
a + b + c = 100%;

A is B is C is selected from the group consisting of:

(I) ;

(II) ; and, (III) combinations thereof, wherein D is OH, halide, OR4, NH2, NHR3, OM', or OM'';
E is the residue of the reaction of at least one Lewis Acid with the D substituent of monomer unit B;
R1 represents proton, C1 -C24 alkyl group, or C3-C24 cycloalkyl;
R2 represents C1-C24 alkylene group, C3-C24 cycloalkylene, C6-C18 arylene, or C7-C30 alkylarylene;
R3 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl;
R4 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl;
M' represents alkali metal; and M'' represents alkaline-earth metal.

4. A process of manufacturing an immobilized Lewis Acid catalyst comprising the steps of reacting a functional copolymer having repeating monomer units represented by the formula:
--[A]a--[B]d--with a Lewis Acid under reaction conditions effective to produce an immobilized Lewis Acid catalyst comprising polymer having repeating monomer units represented by the structural formula:
--[A]a--[B]b--[C]c--wherein a represents 1 to 99 mole %
b represents 0 to 50 mole %
c represents 1 to 99 mole %
a + b + c = 100%
d represents b + c A is B is C is selected from the group consisting of:

(I) ;

(II) ; and' (III) combinations thereof, wherein D is OH, halide, OR4, NH2, NHR3, OM', or OM'';
E is the residue of the reaction of at least one Lewis Acid with the D substituent of monomer unit B;
R1 represents proton, C1-C24 alkyl group, or C3-C24 cycloalkyl;
R2 represents C1-C24 alkylene group, C3-C24 cycloalkylene, C6-C18 arylene, or C7-C30 alkylarylene;
R3 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl;

R4 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl;
M' represents alkali metal; and M'' represents alkaline-earth metal.

5. The process of claim 4 wherein in the functionalized copolymer, [D] is OM' or OM'' wherein M' = alkali metal and M'' = alkaline-earth metal and the Lewis Acid is BF3.

6. A process for alkylating a substrate selected from the group consisting of olefin, alkane, alkyl halide, aromatic compound, and hydroxy aromatic compound with an alkylating agent selected from at least one member of the group consisting of olefin, alkane, and alkyl halide which comprises contacting a mixture of substrate and alkylating agent in the presence of immobilized Lewis Acid catalyst in a manner and under conditions sufficient to alkylate the substrate with the alkylating agent subject to the priviso that the alkylating agent is selected to be different from the substrate employed; and wherein the immobilized catalyst comprises polymer having at least one Lewis Acid immobilized within the structure therein, said polymer having monomer units represented by the structural formula:
--[A]a--[B]b--[C]c--wherein a represents 1 to 99 mole %
b represents 0 to 50 mole %
c represents 1 to 99 mole %
a + b + c = 100%;

A is B is C is selected from the group consisting of:

(I) ;

(II) ; and, (III) combinations thereof, wherein D is OH, halide, OR4, NH2, NHR3, OM', or OM'';
E is the residue of the reaction of at least one Lewis Acid with the D substituent of monomer unit B;
R1 represents proton, C1-C24 alkyl group, or C3-C24 cycloalkyl;
R2 represents C1-C24 alkylene group, C3-C24 cycloalkylene, C6-C18 arylene, or C7-C30 alkylarylene;
R3 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl;
R4 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl;

M' represents alkali metal; and M'' represents alkaline-earth metal.

7. The process of claim 6 wherein an aromatic compound is alkylated.

8. The process of claim 6 wherein a hydroxyaromatic compound is alkylated.

9. The process of claims 7 or 8 wherein the alkylating agent is an alkane.

10. The process of claims 7 or 8 wherein the alkylating agent is an an olefin.

11. The process of claims 7 or 8 wherein the alkylating agent is alkyl halide.

12. An immobilized Lewis Acid catalyst composition comprising a solid polymer having boron fluoride immobilized within the structure therein, said polymer having monomer units represented by the structural formula:
--[A]a--[B]b--[C]c--wherein a represents 1 to 99 mole %
b represents 0 to 50 mole %
c represents 1 to 99 mole %
a + b + c = 100%;

A is B is C is selected from the group consisting of:

(I) ;

(II) ; and, (III) combinations thereof, wherein D is OH, halide, OR4, NH2, NHR3, OM', or OM'';
R1 represents proton, C1-C24 alkyl group, or C3-C24 cyclo- alkyl, R2 represents C1-C24 alkylene group, C3-C24 cycloalkylene, C6-C18 arylene, or C7-C30 alkylarylene;
R3 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl;
R4 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl;
M' represents alkali metal; and M'' represents alkaline-earth metal.

13. A cationically polymerized polymer, having a number average molecular weight of from 300 to 1,000,000 and a molecular weight distribution from about 1.1 to 8.0, the polymer made by a process for polymerizing cationically polymerizable monomer comprising contacting said monomer with a catalytically effective amount of an immobilized Lewis Acid catalyst in a manner and under conditions sufficient to polymerize said monomer, wherein said immobilized catalyst comprises an immobilizing polymer having at least one Lewis Acid immobilized within the structure therein, said polymer having monomer units represented by the structural formula:
--[A]a--[B]b--[C]c--wherein a represents 1 to 99 mole %
b represents 0 to 50 mole %
c represents 1 to 99 mole %
a + b + c = 100%;

A is B is C is selected from the group consisting of:

(I) ;

(II) ; and, (III) combinations thereof, wherein D is OH, halide, OR4, NH2, NHR3, OM', or OM'';
E is the residue of the reaction of at least one Lewis Acid with the D substituent of monomer unit B;
R1 represents proton, C1-C24 alkyl group, or C3-C24 cycloalkyl;
R2 represents C1-C24 alkylene group, C3-C24 cycloalkylene, C6-C18 arylene, or C7-C30 alkylarylene;
R3 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl;
R4 represents C1-C24 alkyl, C3-C24 cycloalkyl, C1-C24 aryl, or C7-C30 alkylaryl;
M' represents alkali metal; and M'' represents alkaline-earth metal.

14. The cationically polymerized polymer of claim 13 having a molecular weight of from 300 to 500,000.

15. The cationically polymerized polymer of claim 14 wherein the polymer has a molecular weight of from 500 to 100,000.

16. The cationically polymerized polymer of claim 15 wherein having a molecular weight of from 500 to 25,000.

17. The cationically polymerized polymer of claim 16 having a molecular weight of from 500 to 5,000.

18. The cationically polymerized polymer of claim 16 having a molecular weight of from 10,000 to 100,000.

19. The immobilized catalyst of any one of claims 1, 3, 4, 6, 12 or 13 wherein said monomer unit A
is derived from propylene, 1-butene, ethylene and mixtures thereof.

20. The immobilized catalyst of claim 19, wherein monomer unit A is derived from propylene.

21. The immobilized catalyst of claim 19, wherein monomer unit A is derived from 1-butene.

22. The immobilized catalyst of any one of claims 1, 3, 4, 6, 12 or 13 wherein monomer unit [C]
is:

;

23. The immobilized catalyst of any one of claims 1, 3, 4, 6, 12 or 13, wherein E is derived from Lewis Acid selected from the group consisting of boron halides, aluminum halides, alkyl aluminum halides, titanium halides and combinations thereof.

24. The immobilized catalyst of any one of claims 1, 3, 4, 6, 12 or 13 wherein the carbon content of R2 is C3 to about C20 alkylene.

25. The immobilized catalyst of any one of claims 1, 3, 4, 6, 12 or 13 wherein b is 0 mole %.

26. The immobilized catalyst of any one of claims 1, 3, 4, 6, 12 or 13 wherein R2 is a C3 to C5 alkylene group.

27. The immobilized catalyst of any one of claims 1, 3, 4, 6, 12 or 13 being a solid.

28. The immobilized catalyst of any one of claims 1, 3, 4, 6, 12 or 13 in the form of a particle having a particle size distribution of from 0.001 to 1.0 mm.

29. The immobilized catalyst of claim 28 having a particle size distribution of from 0.01 to 0.5 mm.

30. The immobilized catalyst of any one of claims 1, 12 or 13 which is coated on a solid substrate.

31. The immobilized catalyst of claim 30 wherein the catalyst is coated on said substrate by extrusion.

32. The immobilized catalyst of claim 30 wherein the catalyst is coated on the substrate by molding.

33. The immobilized catalyst of claim 30 wherein the substrate is the inner wall of a polymerization reactor.

34. Immobilized catalyst of any one of claims 1, 12 or 13 wherein the substrate comprises at least one member of the group consisting of glass, glass fiber, metal plastic including thermoplastic, ceramic, carbon, and mixtures thereof.

35. The cationically polymerizable monomer of claims 3 or 13 wherein said monomer comprises at least one member selected from the group consisting of isobutene, 1-butene and 2-butene, styrenes, propylene, ethylene, dienes and combinations thereof.

36. The cationically polymerizable monomer of claims 3 or 13 wherein said monomer comprises isobutene.

37. The cationically polymerizable monomer of claims 3 or 13 wherein said monomer comprises at least one member selected from the group consisting of 1-butene and 2-butene.

38. The polymer of claims 3 or 13 wherein said polymer comprises at least one member selected from the group consisting of poly(1-butene), poly-n-butene, poly(2-butene), polyethylene, polypropylene, polystyrene, polybutadiene and combinations thereof.

39. Any one of claims 3 or 13, wherein polymerization is conducted in the presence of at least one Lewis Acid cocatalyst.

40. Claim 39 wherein polymerization is conducted by premixing cocatalyst with polymerizable monomer prior to entering a polymerization reactor.

41. Claim 39 wherein the cocatalyst is selected from the group consisting of HCl, HBr, and H2O.

42. Any one of claims 3 or 13 wherein polymerization is conducted in a continuous reactor.

43. Any one of claims 3 or 13 wherein polymerization is conducted in a stirred tank reactor.

44. Any one of claims 3 or 13 wherein polymerization is conducted in a tubular reactor.

45. Any one of claims 3 or 13 wherein polymerization is conducted in a batch process.

46. Any one of claims 3 or 13 wherein polymerization is conducted in a semi-continuous process.

47. Any one of claims 3 or 13 wherein polymerization is conducted in a fluidized bed reactor and the immobilized catalyst is fluidized.

48. Any one of claims 3 or 13 wherein at least one monomer stream is fed to a reactor containing said immobilized catalyst, said monomer stream containing at least one cationically polymerizable monomer, and wherein at least one discharge stream is removed from said reactor, the discharge stream containing polymer and unreacted monomer.

49. Any one of claims 1, 3, 4, 6, 12 or 13 wherein said immobilized catalyst is derived from a functionalized copolymer having a number average molecular weight of from 3,000 to 10,000,000 and having the structural formula wherein A, B and a are defined above and d represents about 1 to about 99 mole %, and being equal to the sum of b + c.

50. Claim 49 wherein the functionalized polymer has a number average molecular weight of from 3,000 to 100,000.

51. The process of claim 3 wherein the polymerization is conducted in the presence of a catalyst.

52. The process of claim 51 wherein the solvent is selected from the group consisting of polar and non-polar solvents.

53. The process of claim 52 wherein the solvent is a polar solvent.

54. The process of claim 53 wherein the solvent is methylene dichloride.

55. The process of any one of claims 3 or 13 wherein the polymerization is conducted at a temperature of from -30°C to +50°C.

56. The cationically polymerized polymer of claim 13 wherein the immobilized catalyst is derived from a Lewis Acid selected from the group consisting of ethylene aluminum dihalide, diethylene aluminum halide,

57. The cationically polymerized polymer of claim 56 wherein the Lewis Acid is selected from the group consisting of ethyl aluminum dichloride, diethyl aluminum chloride, and BF3.