WO2003000750A1

WO2003000750A1 - Polymerization processes using a highly active catalyst

Info

Publication number: WO2003000750A1
Application number: PCT/US2002/019965
Authority: WO
Inventors: Eugene Y. Chen; Debashis Chakraborty
Original assignee: Colorado State University Research Foundation
Priority date: 2001-06-20
Filing date: 2002-06-20
Publication date: 2003-01-03

Abstract

A process for polymerizing an epoxide or olefin in the presence of a catalyst composed of boron, aluminum or gallium and a ligand selected from a halogenated aryl, halogenated aryloxy, halogenated biaryl, halogenated biaryloxy, halogenated arylene, or a mixture thereof does not require the removal of the catalyst from the polymerized product and is sufficiently versatile for use with myriad initiators.

Description

POLYMERIZATION PROCESSES USING A HIGHLY ACTIVE

CATALYST

CROSS-REFERENCES TO RELATED APPLICATIONS [01] This application claims the priority benefit of U.S. Provisional Application No. 60/299,631, filed June 20, 2001, which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION [02] The present invention provides a method for polymerizing epoxides and olefins.

BACKGROUND OF THE INVENTION [03] Polyethers made from epoxides (i.e., al ylene oxides) are well known and useful in a number of applications, such as detergent and cleaner compositions, oil well drilling fluids, inks, metal working fluids, lubricants in paper coating compositions, ceramics manufacturing, chemical intermediates for nonionic surfactants which in turn are used in cosmetics, textiles and chemical processing, cellular and noncellular polyurethanes, chemical intermediates for esters which are used in textile spin finishes, cosmetic agents, and as foam control agents for a wide variety of processes. These polymers may have no more than one oxyalkylene group in succession, or be a higher molecular weight polymer containing one or more long chains of consecutive oxyalkylene groups. [04] Polyethers of this type are commonly made through an anionic polymerization process, whereby the epoxide is combined with an initiator compound and a strongly basic catalyst such as potassium hydroxide or certain organic amines. The initiator compound contains one or more oxyalkylatable groups such as hydroxyl, thiol, carboxylic acid and the like. The initiator compound determines the functionality (i.e., number of hydroxyl groups/molecule of product) and in some cases may introduce some desired functional group into the product.

[05] There are some disadvantages of polymerizing epoxides using these strongly basic catalysts, for example, the basic catalyst usually must be removed from the product before it is used, which increases manufacturing costs. [06] In addition, some kinds of initiator compounds cannot be alkoxylated using strongly basic catalysts, because they contain base-sensitive functional groups. For example, initiators containing certain types of alkenyl or alkynyl groups undergo a side reaction in which the alkenyl or alkynyl group will "migrate" along the molecular chain, so that the unsaturation in the polyether is at a different place than it was on the initiator. This is of particular concern when terminal unsaturation is desired. Often, unsaturation that is in a terminal position on the initiator migrates to a non-terminal position during the alkoxylation reaction.

[07] Unsaturated compounds in which a triple bond is adjacent to a hydroxyl- substituted carbon atom are prone to decomposing during the alkoxylation reaction. Many compounds of this type are reaction products of acetylene with a ketone such as acetone or an aldehyde such as acetaldehyde. Alkali metal or alkaline earth bases can cause these initiators to decompose to regenerate acetylene. Acetylene is an explosion hazard. [08] In order to try to avoid these problems, Lewis acids such as boron trifmoride- diethyl etherate and organic amines such as triethylamine have been tried. However, some of these catalysts tend to promote the formation of large amounts of by-products, especially when it is attempted to add three or more moles of alkylene oxide per equivalent of initiator compound. The Lewis acid catalysts tend to catalyze "back-biting" reactions where the growing polymer chain reacts with itself. The reactions form cyclic ethers such as dioxane, dimethyldioxane and various crown ethers. These cannot be removed easily from the desired product, and so the product cannot be used in many applications. [09] Thus, there is a need for a method for producing polyethers using non-basic catalysts which produces polyethers in good yield with low levels of by-products.

SUMMARY OF THE INVENTION [10] One aspect of the present invention provides a process for polymerizing an epoxide. The process comprises contacting the epoxide with a polymerization catalyst to produce a polyether, i.e., poly(alkylene oxide) polymer. The polymerization catalyst comprises (a) a metal selected from the group consisting of boron, aluminum, and gallium; and (b) a ligand selected from the group consisting of halogenated aryl, halogenated aryloxy, halogenated biaryl, halogenated biaryloxy, halogenated arylene, and a mixture thereof. [11] Another aspect of the present invention provides a process for producing a polyolefin by polymerizing an olefin in the presence of a polymerization catalyst. The polymerization catalyst for production of the polyolefin comprises (a) aluminum; and (b) a ligand selected from the group consisting of halogenated aryl, halogenated aryloxy, halogenated biaryl, halogenated biaryloxy, halogenated arylene, and a mixture thereof. [12] In another aspect, the present invention is to effectively end-capping polyether polyols containing a secondary hydroxyl group with ethylene oxide using a catalyst of the present invention. Preferably, the polyether polyol is prepared using a non-finishing catalyst, such as a double metal cyanide (DMC) catalyst. [13] In a further aspect, the catalysts of the present invention can be used to add alkylene oxides to monomeric initiators containing two or more active hydrogen atoms, such as glycerin, sorbitol, sucrose, trimethylol propane, etc. The resulting products can be further reacted with other alkylene oxide monomers to provide higher molecular weight polyols. [14] Surprisingly and unexpectedly, the present inventor has found that polymerization catalysts of the present invention have a high turn-over rate. Furthermore, polymerization catalysts of the present invention produce polymers at a significantly higher yield then similar catalysts having non-halogenated ligands.

BRIEF DESCRIPTION OF THE DRAWINGS [15] Figure 1 shows some of the representative polymerization catalysts of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

[16] "Alkyl" refers to a saturated linear or branched monovalent hydrocarbon moiety having from one to twenty carbon atoms, preferably one to six carbon atoms. Exemplary alkyl groups include methyl, ethyl, π-propyl, 2-propyl, tert-butyl, pentyl, and the like.

[17] "Alkoxy" refers to a moiety of the formula -OR , where R^b is alkyl as defined above.

[18] "Aryl" refers to a monovalent monocyclic or bicyclic aromatic hydrocarbon moiety of six to ten carbon ring atoms. The aryl group can be optionally substituted with one or more substituents selected from alkyl, haloalkyl, and alkoxy group. The term aryl includes, but is not limited to, phenyl, naphthyl, and the like.

[19] "Arylene" refers to a divalent monocyclic or bicyclic aromatic hydrocarbon moiety of six to ten carbon ring atoms. The arylene group can be optionally substituted with one or more substituents selected from alkyl, haloalkyl, and alkoxy group. The term aryl includes, but is not limited to, phenylene, naphthylene, and the like. When one or more number is present in front of the term "arylene", the numbers indicate relative positions of the substituents. For example, 1,2-phenylene and 1,4-phenylene refer to divalent phenyl groups in which two substituents attached to the arylene are at positions 1,2- and 1,4- relative to each other, respectively.

[20] "Aryloxy" refers to a moiety of the formula -OR^a, where R^a is aryl as defined above.

[21] "Biaryl" refers to an aryl group which is substituted with another aryl group.

Exemplary aryl groups include biphenyl, binaphthyl, phenylnaphthyl, and the like.

[22] "Halogenated" refers to a moiety in which one or more hydrogen has been replace with halide, such as chlorine, bromine, or preferably fluorine. [23] "Perfluorinated" means all of the hydrogen atoms of a moiety have been replaced with fluorine.

[24] "Turn-over rate" refers to moles of monomers consumed per mole of a polymerization catalyst per hour. The turn-over rate is typically measured in the absence of any significant amount of solvent. [25] As used herein, the terms "those defined above" and "those defined herein" when referring to a variable incorporates by reference the broad definition of the variable as well as preferred, more preferred and most preferred definitions, if any.

Polymerization Catalyst

[26] Polymerization catalysts of the present invention are useful in polymerization reactions of epoxides and olefins. Unlike conventional catalysts, present inventors have found that the catalysts of the present invention have a high turn-over rate thereby requiring only a small amount of the catalyst and/or a short polymerization reaction time. Furthermore, polymerization catalysts of the present invention produces polymers at a significantly higher yield compared to similar catalysts having non-halogenated ligands. [27] While the present invention is generally described in connection with using the polymerization catalysts described herein, methods of the present invention are not limited to this composition. For example, methods of the present invention can also include one or more initiators which are conventionally known to one skilled in the art in producing polyethers from epoxides. Furthermore, methods of the present invention can also include other components which are typically used in polymerization reactions, such as stabilizers, surfactants, coloring agents, cross-linkers, etc. [28] Polymerization catalysts of the present invention comprise a metal and a halogenated aromatic ligand. The aromatic ligand can be attached directed to the metal or it can be attached to the metal through an oxygen atom.

[29] Preferably, the metal is a Group III metal, e.g., boron, aluminum, gallium, indium, and thallium. More preferably, the metal is selected from the group consisting of boron, aluminum, and gallium. For polymerization of epoxides, the metal is preferably boron or aluminum. For polymerization of olefins, the metal is preferably aluminum. [30] Preferably, the ligand is selected from the group consisting of halogenated aryl, halogenated aryloxy, halogenated biaryl, halogenated biaryloxy, halogenated arylene, and a mixture thereof. More preferably, at least one of the ligand is perhalogenated moiety described above. Still more preferably, at least one of the ligand is perfluorinated moiety described above. And most preferably, all of the ligands are perfluorinated moiety described above.

[31] In one particular embodiment, the polymerization catalyst is of the formula: (X)_a-M-[(0)_b-Ar¹]_c

I wherein

M is B, Al or Ga; each X is independently hydrogen or halide; preferably, X is hydrogen, bromo, chloro, or fluoro; a is an integer from 0 to 2; preferably, a is 0; each b is independently 0 or 1 ; each Ar is independently aryl, halogenated aryl, biaryl, or halogenated biaryl, provided at least one Ar¹ is halogenated aryl or halogenated biaryl; and c is an integer of at least 1; preferably c is 3, provided the sum of a and c is equal to the oxidation state of M.

[32] In one embodiment, a is 0. Thus, all the ligands on the metal are aromatic moieties. Preferably, each Ar¹ is independently halogenated aryl or halogenated biaryl. More preferably, each Ar¹ is independently perfluorinated aryl or perfluorinated biaryl. Still more prefrably, each Ar¹ is independently pentylfluorophenyl, 2-pentafluorophenyl-3, 4,5,6- tetrafluorophenyl, or l,3,4,5,6,7,8-heptafluoronaphth-2-yl.

[33] In another embodiment of the present invention, the polymerization catalyst is of the formula: [Ar¹-(O)_b]_c-M¹-Ar²-M²-[(O)_d-Ar³]_e π wherein b, c, and Ar¹ are those defined herein; each of M¹ and M² is independently B, Al, or Ga; preferably M¹ and M² are the same; each d is independently 0 or 1; each Ar is independently aryl, halogenated aryl, biaryl, or halogenated biaryl; and Ar² is arylene or halogenated arylene; each e is independently an integer of at least 1, provided at least one of Ar¹ and Ar³ is halogenated aryl or Ar² is halogenated arylene, and provided the sum of c+1 and the sum of e+1 are equal to the oxidation state of appropriate M, i.e., metal to which respective ligands having variable c and e are attached to. [34] In particular one embodiment, c and e are 2.

[35] In another embodiment, each of Ar and Ar is independently halogenated aryl. Preferably, Ar and Ar are pentafluorophenyl. [36] Yet in another embodiment, b and d are 0.

[37] Still in another embodiment, Ar is 1,2-substituted phenylene, 1,2-substituted tetrafluorophenylene, 1,4-substituted phenylene, or 1,4-substituted tetrafluorophenylene. [38] Yet in another embodiment of the present invention, the polymerization catalyst is of the formula:

wherein M¹, M², b, d, Ar¹, Ar², and Ar³ are those defined herein; and

Ar⁴ is independently arylene or halogenated arylene; provided at least one of Ar¹ or Ar³ is halogenated aryl or one of Ar² or Ar⁴ is halogenated arylene.

[39] In one particular embodiment, each of Ar² and Ar⁴ is independently 1,2- substituted phenylene, 1,2-substituted tetrafluorophenylene, 1,4-substituted phenylene, or

1,4-substituted tetrafluorophenylene. Preferably, Ar² and Ar⁴ are 1,2-substituted tetrafluorophenylene. [40] Still further, combinations of the preferred groups described herein will form other preferred embodiments. In this manner, variety of preferred compounds are embodied within the present invention.

[41] Some of the representative polymerization catalysts are shown in Figure 1, where M is as defined herein. For polymerization of epoxides, M is preferably boron or aluminum. For polymerization of olefins, M is preferably aluminum. [42] As described above, polymerization catalysts of the present invention are useful in producing polyethers from epoxides such as, but are not limited to, ethylene oxide, propylene oxide, butylene oxide, and cyclohexene oxide. In addition, polymerization catalysts of the present invention are also useful in producing polymers from olefins, such as styrene, isobutylene and vinyl ether. The catalysts are also useful in capping of polyalkylene oxides and polyoxystyrene polymers with ethylene oxide (EO), examples of such polymers include polypropylene, polybutylene, polypropylene/ polybutylene polymers or a mixture thereof. Preferably the catalyst is used to end-cap a polyoxypropylene polymer with EO. Process conditions for end-capping with EO are well known in the art.

[43] Typically, the turn-over rate of the polymerization catalysts of the present invention is at least about 500 per hour, preferably at least about 1,000, more preferably at least about 2,000, and most preferably at least about 4,000. Moreover, since the polymerization catalysts of the present invention have such a high turn-over rate, the amount of the polymerization catalyst used can be significantly less than the stoichiometric amount, i.e., less than one equivalent, of the compound. Typically, the amount of polymerization catalyst used is less than about 0.1 mole% of the epoxide, preferably less than about 0.01 mole%, and more preferably less than about 0.001 mole . [44] However, it should be appreciated that the present invention is not limited to the above described turn-over rate and catalyst concentration. Generally, the tum-over rate and the amount of catalyst used in a given reaction depends on a variety of factors, including the nature of the substrate, reaction solvent, the amount and/or the nature of any impurities that may be present in the reagents and/or the solvent, etc. Typically, for cyclohexene oxide polymerization, the preferred turn-over rate is at least about 50,000, more preferably at least about 100,000, and most preferably at least about 150,000. For polymerization of styrene, the turn-over rate is preferably at least about 20,000, more preferably at least about 40,000, and most preferably at least about 60,000. And for polymerization of propylene oxide, the turn-over rate is preferably at least about 2000, more preferably at least about 3,000, and most preferably at least about 4,000. [45] The catalysts are typically prepared from reaction of group El metal halides, alkyls, or alkoxides with an appropriate halogenated aromatic organic ligand in neutral form or anionic form complexed with other metals such as Li, Mg, Sn, etc. Hydrocarbon and ether solvents are commonly used for the catalyst preparation. The catalysts are generally isolated and purified by recrystallization or sublimation.

[46] The invention includes a process for making an epoxide polymer. This process comprising polymerizing an epoxide in the present of a catalyst of the present invention. Preferred epoxides are ethylene oxide propylene oxide, butylene oxides, styrene oxide, and the like, and mixtures thereof. The process can be used to make random or block copolymers. The epoxide polymer can be, for example, a polyether polyol derived from the polymerization of an epoxide in the presence of a hydroxyl group containing initiator. Process conditions for such polymerization reactions are well known in the art. [47] Polymers produced by a process of the present invention are useful in a variety of applications, including, but not limited to producing polyurethanes. Polyurethanes can be produced by reacting a polyol which is prepared according to the process described herein with an isocyanate. Processes for producing polyurethanes is well known to one of ordinary skill in the art. For example, see U.S. Patent Nos. 5,010,117, issued to Herrington et al., 3,535,307, issued to Moss et al., and 4,687,851, issued to Laughner, and EP Publication No. 0 394 487 by Takeyasu et al., which are incorporated herein by reference in their entirety.

EXAMPLES

[48] The present invention will now be described in detail in reference to a method for producing a polyol from propylene oxide, which is used frequently in a polyurethane synthesis. However, it should be appreciated that methods for present invention can be used to produce other polyols from other epoxides and catalysts. Moreover, the following preparations and examples are given to enable those skilled in the art to more clearly understand and to practice the present invention. They should not be considered as limiting the scope of the invention, but merely as being illustrative and representative thereof. [49] All syntheses and manipulations of air- and moisture-sensitive materials were carried out in flamed Schlenk-type glassware on a dual-manifold Schlenk line or in an inert atmosphere (argon) glove box. Organic solvents were first saturated with nitrogen and then dried by passage through activated alumina and Q-5™ catalyst (Englehardt Chemicals Inc.) prior to use. Deuterated benzene and toluene were dried over sodium/potassium alloy and distilled and/or filtered prior to use. CDC1₃ was dried over activated Davison 4A molecular sieves. Propylene oxide and styrene monomers were degassed and dried over CaH₂ overnight, and then freshly vaccum-distilled before use. NMR spectra were recorded on either Varian Inova 300 (FT 300 MHz, 1H; 75 MHz, ¹³C; 282 MHz, ¹⁹F) or Varian Inova 400 spectrometer. Chemical shifts for 1H and ¹³C spectra were referenced to internal solvent resonances and reported relative to tetramethylsilane. ¹⁹F NMR spectra were referenced to external CFC1₃. Tris(perfluorophenyl)borane B(C₆F₅)₃ was obtained as from Boulder Scientific Company and used without further purification for preparative reactions, or purified by recrystallization from hexane at -35 °C for NMR-scale reactions. Trimethylaluminum (AlMe ) in toluene or hexanes, aluminum tri-isopropoxide (Al(O^!Pr)₃), and pentafluorophenol were purchased from Aldrich Chemical Co. AlCO'Prfo was freshly vacuum distilled prior to use. MMAO (2.2 weight Al, d = 0.69 g/mL, 0.56 M in heptane) was purchased from Akzo-Nobel Co.

Example 1

[50] This example illustrates a method for producing tris(perfluorophenyl)alane catalyst.

[51] Tris(perfluorophenyl)alane (A1(C₆F₅)₃ as a toluene adduct) catalyst was prepared by exchange reaction between tris(perfluorophenyl)borane and trimethylaluminum as disclosed in U.S. Patent No. 5,602269, issued to Biagini, et al., which is incorporated herein by reference in its entirety. Example 2

[52] This example illustrates a method for producing a mixture of catalysts.

[53] A mixture of B(C₆F₅)₃ and AlMe₃ was prepared by mixing B(C₆F₅)₃ and

AlMe₃ in 2 mL of toluene in B/Al ratios ranging from 0.2 to 5 by stirring at room temperature for 10 minutes. Example 3

[54] This example illustrates a method for producing Al(OC₆F₅)₃.

[55] A mixture of pentafluorophenol and trimethyaluminum in a 3: 1 ratio in toluene was stirred first at room temperature for 3 h, second under mild refluxing for 14 h, and finally under vigorous refluxing for 4 h. The solvent was removed under reduced pressure and residue was washed with hexane to produce Al(OC₆F₅)₃ as a yellow solid after drying in vacuo. Yield: 60%. NMR spectra indicated a dimeric structure in solution. ¹⁹F NMR (C₇D₈, 23 °C): 6 -154.93 (t, ³J_F-F = 21.2 Hz, 2 F, p-F-bridging), -158.11 (t, ³J_F._F = 21.5 Hz, 4 F, -F-terminal), -159.01 (d, ³J_F-F = 21.5 Hz, 4 F, σ-F-bridging), -163.54 (m, 8 F, o-F- terminal + p-F-terminal), -166.39 (pent, 4 F, m-F-bridging). ¹⁹F NMR (C₆D₆, 23 °C): δ - 155.33, -158.60 (t), -159.80 (d), -164.08 (t), -164.36 (d), -166.87 (t).

Example 4

[56] This example illustrates polymerization of propylene oxide using variety of polymerization catalysts of the present invention and the effect of an initiator in the polymer yield.

[57] Propylene oxide polymerizations were performed in 50 mL Schlenk tubes with a septum and an external temperature-controlled bath on a high vacuum line or in a wide mouth bottle in a glove box. In a typical procedure, to 5.0 mL (71.5 mmol) propylene oxide was added 7.4 mg catalyst B(C₆F₅)₃ (monomer/catalyst ratio =5,000). Addition of the solid catalyst or in toluene solution caused monomer to reflux vigorously. After a measured time interval (typically 2 h), excess of the monomer was removed under reduced pressure to afford the polymer as a sticky, colorless oil. Results are summarized in Table 1.

Table 1. Results for Ring-Opening Polymerization of Propylene Oxide (room temperature,

a. comparative examples, b. initiator is methanol. c. initiator is 1,4-butanediol. d. initiator is 2,5-hexanediol. e. initiator is benzyl alcohol. /. initiator is C₆H₅COOH. g. initiator is C₆H₅OH. h. initiator is H₂O.

Example 5.

[58] This example illustrates polymerization of cyclohexene oxide using variety of polymerization catalysts of the present invention. [59] In a glove box, a catalyst (9.88 micromole ) was dissolved in 2 mL toluene in a Schlenk tube. This tube was taken out of the box and attached to the high vacuum line. Cyclohexene oxide (4.94 mmol, monomer/catalyst ratio = 500) was then quickly injected into the solution via a gas-tight syringe once the external bath temperature was stabilized. The polymerization was terminated by addition of acidic methanol after the measured time interval. The polymer product was precipitated into 50 mL methanol, filtered, washed with methanol, and dried in a vacuum oven at 50 °C overnight to a constant weight. Results are summarized in Table 2 below: Table 2. Results for Ring-Opening Polymerization of Cyclohexene Oxide

Catalyst Monomer/ Polymerization Polymerization Polymer yield Turn-over rate Catalyst ratio temperature (°C) time (min) (isolated, %) (h^'1)

B(C₆F₅)₃ 500 0 0.25 100 120 000

A1(C₆F₅)₃ 500 0 0.17 88 158 000

A1(C₆F₅)₃ 500 -78 0.17 88 158 000

AΪ(OC₆F₅)₃ 50θ^" ^"23 1.0 96 28 800

Al(OC₆F₅)₃ 500 0 1.67 97 17 400

Al(OC₆F₅)₃ 500 -78 38.8 27 210

Al(O'Pr)₃* 500^" 23 60^{" '} trace 0

AlMe₃* 250 -20 1440 trace 0

AlEt₃* 250 -20 1440 87 9

ZnEt₂ * 100 80 1440 47 2 * comparative examples.

Example 6

[60] This example illustrates polymerization of styrene using variety of polymerization catalysts of the present invention.

[61] A catalyst (17.4 μmol) was dissolved in 5 mL toluene and styrene (2 mL, 17.4 mmol, monomer/catalyst ratio = 1000/1) was added via syringe. Stirring was stopped within a minute and the polymerization was terminated by addition of acidic methanol. The polymer product was precipitated into 50 mL methanol, filtered, washed with methanol, and dried in a vacuum oven at 50 °C overnight to a constant weight. Results are summarized in

Table 3. Table 3. Results for Pol merization of St rene room tem erature)

comparative examples. [62] As Table 3 shows, polymerization catalysts of the present invention comprising aluminum metal are particularly useful in olefin polymerization reaction.

Example 7

[63] This example illustrates end-capping of a polyoxypropylene polyol with ethylene oxide.

[64] Catalysts were tested for EO capping in a 300 ml Parr Raeactor. The apparatus was controlled via a Camile laboratory system. The reactor is equipped with a hollow agitator shaft and a gas dispersion impeller.

[65] In a typical experiment 60 to 82 grams of initiator and an aliquot of catalyst were placed into the clean reactor contained in a glove box to eliminate moist air contamination. The initiator used was a 4000 Mw glycerine initiated all PO triol produced with Double Metal Cyanide (DMC) catalyst and the DMC removed. The reactor was first purged with Nitrogen at 200 cc/min for about 5 minutes at room temperature. The reactor was slowly heated to reaction temperature (60 to 110°C over 1 hour with the N₂ sparging.

[66] Ethylene oxide was added to the reactor initially maintaining the reactor via cooling control. The pressure was then maintained at 30 to 60 psig set point with additional

EO. The gaseous EO feed take was maintained with a pad of at least 60 psig nitrogen. At termination of the feed, the system was vented and the product removed. The results of the

EO capping are given in Table 4.

Table 4. EO ca in data

[67] The rate is measured as ml EO/hr/1000 ppm catalyst. NMR analysis of the product polymer was used to estimate the extent of the EO capping.

[68] The foregoing discussion of the invention has been presented for purposes of illustration and description. The foregoing is not intended to limit the invention to the form or forms disclosed herein. Although the description of the invention has included description of one or more embodiments and certain variations and modifications, other variations and modifications are within the scope of the invention, e.g., as may be within the skill and knowledge of those in the art, after understanding the present disclosure. It is intended to obtain rights which include alternative embodiments to the extent permitted, including alternate, interchangeable and/or equivalent structures, functions, ranges or steps to those claimed, whether or not such alternate, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes.

Claims

WHAT IS CLAIMED IS:

1. A process for polymerizing an epoxide, wherein said process comprises contacting the epoxide with a polymerization catalyst to produce a polyol polymer, wherein the polymerization catalyst comprises: (a) a metal selected from the group consisting of boron, aluminum, and gallium; and (b) a ligand selected from the group consisting of halogenated aryl, halogenated aryloxy, halogenated biaryl, halogenated biaryloxy, halogenated arylene, and a mixture thereof.

2. The process of Claim 1, wherein the polymerization catalyst is of the formula: (X)_a-M-[(O)_b-Ar¹]_c wherein M is B, Al or Ga; each X is independently hydrogen or halide; a is an integer from 0 to 2; each b is independently 0 or 1; each Ar¹ is independently aryl, halogenated aryl, biaryl, or halogenated biaryl, provided at least one Ar¹ is halogenated aryl or halogenated biaryl; and c is an integer of at least 1 , provided the sum of a and c is equal to the oxidation state of M.

3. The process of Claim 2, wherein M is B or Al.

4. The process of Claim 3, wherein X is hydrogen, bromo, chloro, or fluoro.

5. The process of Claim 3, wherein a is 0.

6. The process of Claim 5, wherein each Ar¹ is independently halogenated aryl or halogenated biaryl.

7. The process of Claim 6, wherein each Ar¹ is independently perfluorinated aryl or perfluorinated biaryl.

8. The process of Claim 6, wherein each Ar¹ is independently pentylfluorophenyl, 2-pentafluorophenyl-3,4,5,6-tetrafluorophenyl, or 1,3,4,5,6,7,8- heptafluoronaphth-2-yl.

9. The process of Claim 6, wherein c is 3.

10. The process of Claim 9, wherein b is 0.

11. The process of Claim 9, wherein b is 1.

12. The process of Claim 1, wherein the polymerization catalyst is of the formula: [Ar¹-(O)_b]_c-M¹-Ar²-M²-[(O)_d-Ar³]_e wherein each of M¹ and M² is independently B, Al or Ga; each of b and d is independently 0 or 1 ; each of Ar and Ar is independently aryl, halogenated aryl, biaryl, or halogenated biaryl; and Ar² is arylene or halogenated arylene; each of c and e is independently an integer of at least 1, provided at least one of Ar¹ and Ar³ is halogenated aryl or Ar² is halogenated arylene, and provided the sum of c+1 and the sum of e+1 are equal to the oxidation state of appropriate M.

13. The process of Claim 12, wherein M is B or Al.

14. The process of Claim 13, wherein c and e are 2.

15. The process of Claim 14, wherein each of Ar¹ and Ar³ is independently halogenated aryl.

16. The process of Claim 15, wherein Ar¹ and Ar³ are pentafluorophenyl.

17. The process of Claim 16, wherein b and d are 0.

18. The process of Claim 17, wherein Ar² is 1,2-substituted phenylene, 1,2-substituted tetrafluorophenylene, 1,4-substituted phenylene, or 1,4-substituted tetrafluorophenylene.

19. The process of Claim 1, wherein the polymerization catalyst is of the formula:

wherein each of M¹ and M² is independently B, Al or Ga; each of b and d is independently 0 or 1 ; each of Ar¹ and Ar³ is independently aryl, halogenated aryl, biaryl, or halogenated biaryl; and each of Ar² and Ar is independently arylene or halogenated arylene; provided at least one of Ar¹ or Ar³ is halogenated aryl or one of Ar² or Ar⁴ is halogenated arylene.

20. The process of Claim 19, wherein each of Ar and Ar is independently halogenated aryl.

21. The process of Claim 20, wherein Ar¹ and Ar³ are pentafluorophenyl.

22. The process of Claim 21 , wherein b and d are 0.

23. The process of Claim 22, wherein each of Ar² and Ar⁴ is independently 1,2-substituted phenylene, 1,2-substituted tetrafluorophenylene, 1,4-substituted phenylene, or 1,4-substituted tetrafluorophenylene.

24. The process of Claim 23, wherein Ar² and Ar⁴ are 1,2-substituted tetrafluorophenylene.

25. The process of Claim 1 , wherein the amount of the polymerization catalyst used is less than about 0.1 mole% of the epoxide.

26. A process for producing a polyolefin comprising polymerizing an olefin in the presence of a polymerization catalyst to produce the polyolefin, wherein the polyemrization catalyst comprises: (a) aluminum; and (b) a ligand selected from the group consisting of halogenated aryl, halogenated aryloxy, halogenated biaryl, halogenated biaryloxy, halogenated arylene, and a mixture thereof.

27. The process of Claim 26, wherein the polymerization catalyst is of the formula: (X)_a-Al-[(O)_b-Ar¹]_c wherein each X is independently hydrogen or halide; a is an integer from 0 to 2; each b is independently 0 or 1; each Ar¹ is independently aryl, halogenated aryl, biaryl, or halogenated biaryl, provided at least one Ar¹ is halogenated aryl or halogenated biaryl; and c is an integer of at least 1, provided the sum of a and c is equal to the oxidation state of M.

28. The process of Claim 26, wherein the polymerization catalyst is of the formula:

[Ar¹-(O)_b]₂-Al-Ar²-Al-[(O)_d-Ar³]₂ wherein each of b and d is independently 0 or 1; each of Ar¹ and Ar³ is independently aryl, halogenated aryl, biaryl, or halogenated biaryl; and

Ar is arylene or halogenated arylene; provided at least one of Ar¹ and Ar³ is halogenated aryl or Ar² is halogenated arylene.

29. The process of Claim 26, wherein the polymerization catalyst is of the formula:

wherein each of b and d is independently 0 or 1; each of Ar and Ar is independently aryl, halogenated aryl, biaryl, or halogenated biaryl; and each of Ar² and Ar⁴ is independently arylene or halogenated arylene; provided at least one of Ar¹ or Ar³ is halogenated aryl or one of Ar² or Ar⁴ is halogenated arylene.

30. A process for end-capping a polyether polyol comprising a secondary hydroxyl moiety, said process comprising end-capping the polyether polyol with ethylene oxide using a polymerization catalyst to produce an encapped polyether polyol, wherein the polyether polyol is prepared using a non-finishing catalyst, and wherein the polymerization catalyst comprises: (a) a metal selected from the group consisting of boron, aluminum, and gallium; and (b) a ligand selected from the group consisting of halogenated aryl, halogenated aryloxy, halogenated biaryl, halogenated biaryloxy, halogenated arylene, and a mixture thereof.

31. The process of Claim 30, wherein the polymerization catalyst is of the formula: (X)_a-M-[(O)_b-Ar¹]_c wherein M is B, Al or Ga; each X is independently hydrogen or halide; a is an integer from 0 to 2; each b is independently 0 or 1; each Ar¹ is independently aryl, halogenated aryl, biaryl, or halogenated biaryl, provided at least one Ar¹ is halogenated aryl or halogenated biaryl; and c is an integer of at least 1 , provided the sum of a and c is equal to the oxidation state of M.

32. The process of Claim 30, wherein the polymerization catalyst is of the formula: [Ar¹-(O)_b]_c-M¹-Ar²-M -[(O)_d-Ar³]e wherein each of M¹ and M² is independently B, Al or Ga; each of b and d is independently 0 or 1 ; each of Ar¹ and Ar³ is independently aryl, halogenated aryl, biaryl, or halogenated biaryl; and Ar² is arylene or halogenated arylene; each of c and e is independently an integer of at least 1, provided at least one of Ar¹ and Ar³ is halogenated aryl or Ar² is halogenated arylene, and provided the sum of c+1 and the sum of e+1 are equal to the oxidation state of appropriate M.

33. The process of Claim 30, wherein the polymerization catalyst is of the formula:

wherein each of M¹ and M² is independently B, Al or Ga; each of b and d is independently 0 or 1; each of Ar¹ and Ar³ is independently aryl, halogenated aryl, biaryl, or halogenated biaryl; and each of Ar² and Ar⁴ is independently arylene or halogenated arylene; provided at least one of Ar¹ or Ar³ is halogenated aryl or one of Ar² or Ar⁴ is halogenated arylene.