A compound useful as a cocatalyst or cocatalyst component, especially for use as an addition polymerization catalyst compound, corresponding to the formula:

The present invention relates to compounds that are useful as catalyst components. More particularly the present invention relates to such compounds that are particularly adapted for use in the coordination polymerization of unsaturated compounds comprising an anion containing at least two Lewis basic sites which are coordinated to Lewis acids, and further containing a hydroxyl group or a polar group containing a quiescent reactive functionality. Such compounds are particularly advantageous for use in forming supported polymerization catalysts wherein at least the catalyst activator is chemically attached to a substrate material.
It is previously known in the art to activate Ziegler-Natta polymerization catalysts, particularly such catalysts comprising Group 3-10 metal complexes containing delocalized xcfx80-bonded ligand groups, by the use of Bronsted acid salts capable of transferring a proton to form a cationic derivative or other catalytically active derivative of such Group 3-10 metal complex. Preferred Bronsted acid salts are such compounds containing a cation/anion pair that is capable of rendering the Group 3-10 metal complex catalytically active. Suitable activators comprise fluorinated arylborate anions, such as tetrakis(pentafluorophenyl)borate. Additional suitable anions include sterically shielded diboron anions of the formula:
wherein:
S is hydrogen, alkyl, fluoroalkyl, aryl, or fluoroaryl, ArF is fluoroaryl, and X1 is either hydrogen or halide, disclosed in U.S. Pat. No. 5,447,895. Additional examples include carborane compounds such as are disclosed and claimed in U.S. Pat. No. 5,407,884.
Examples of preferred charge separated (cation/ anion pair) activators are ammonium, sulfonium, or phosphonium salts capable of transferring a hydrogen ion, disclosed in U.S. Pat. No. 5,198,401, U.S. Pat. No. 5,132,380, U.S. Pat. No. 5,470,927 and U.S. Pat. No. 5,153,157, as well as oxidizing salts such as ferrocenium, silver or lead salts, disclosed in U.S. Pat. No. 5,189,192 and U.S. Pat. No. 5,321,106 and strongly Lewis acidic salts such as carbonium or silylium salts, disclosed in U.S. Pat. No. 5,350,723 and U.S. Pat. No. 5,625,087.
Further suitable activators for the above metal complexes include strong Lewis acids including tris(perfluorophenyl)borane and tris(perfluorobiphenyl)borane. The former composition has been previously disclosed for the above stated end use in EP-A-520,732, whereas the latter composition is similarly disclosed by Marks, et al., in J. Am. Chem. Soc., 118, 12451-12452 (1996).
Despite the satisfactory performance of the foregoing catalyst activators under a variety of polymerization conditions, there is still a need for improved cocatalysts for use in the activation of various metal complexes especially under a variety of reaction conditions. Accordingly, it would be desirable if there were provided compounds that could be employed in solution, slurry, gas phase or high pressure polymerizations and under homogeneous or heterogeneous process conditions having improved activation properties. In particular, it would be desirable to provide compounds that may be chemically bonded to support materials to prepare supported catalyst components having improved resistance to solvent removal and loss from the particle surface.
According to the present invention there are now provided compounds useful as catalyst activators corresponding to the formula:
(A*+a)b(Z*J*j)xe2x88x92cd,
wherein:
A* is a cation of from 1 to 80, preferably 1 to 60 atoms, not counting hydrogen atoms, said A* having a charge +a,
Z* is an anion group of from 1 to 50, preferably 1 to 30 atoms, not counting hydrogen atoms, further containing two or more Lewis base sites;
J* independently each occurrence is a Lewis acid of from 1 to 80, preferably 1 to 60 atoms, not counting hydrogen atoms, coordinated to at least one Lewis base site of Z*, and optionally two or more such J* groups may be joined together in a moiety having multiple Lewis acidic functionality,
j is a number from 2 to 12 and
a, b, c, and d are integers from 1 to 3, with the proviso that axc3x97b is equal to cxc3x97d, and provided further that one or more of A*, Z* or J* comprises a hydroxyl group or a polar group containing quiescent reactive functionality.
The foregoing compounds, in particular, those containing quiescent reactive functionality may be utilized in combination with one or more Group 3-10 or Lanthanide metal complexes to form catalyst compositions for polymerization of addition polymerizable monomers, especially ethylenically unsaturated monomers, most preferably, C2-20,000 xcex1-olefins. Additionally, the compounds may be utilized to form latent activators, that is, compounds that may themselves not cause a metal complex to become catalytically active, but which may be converted to such a compound, by, for example, in-situ reaction of the hydroxyl group or quiescent reactive functionality or its derivative with a Lewis acid, especially an aluminum hydrocarbyl compound, or an alkali metal halide or ammonium halide salt. Moreover, the compounds may be deposited onto solid supports, such as by impregnation, surface deposition, physisorption or chemical reaction with the support, reactive functionality of the support, or chemical modifiers associated with the support, to form heterogeneous catalyst components for use in preparing heterogeneous catalyst compositions for use in polymerization of the foregoing monomers.
In one embodiment of the invention, the foregoing compounds are used to form supported catalyst components by reaction of the hydroxyl group thereof with reactive functionality of a support material, or by conversion of the quiescent reactive functionality to a reactive functionality and reaction thereof with reactive functionality of a support material. The resulting supported catalyst components are highly resistant to loss of activator compound in a liquid reaction medium such as occurs in a slurry polymerization. One or more Group 3-10 or Lanthanide metal complexes, preferably a Group 4 metal complex, and additional additives, modifiers and adjuvants may be added to the catalyst component, either before, after or simultaneous with addition of the cocatalyst of the present invention, to form the fully formulated catalyst composition.
Additionally according to the present invention there is provided a catalyst composition for polymerization of an ethylenically unsaturated, polymerizable monomer comprising, in combination, the above described activated derivative compound, a Group 3-10 metal complex that is capable of activation to form an addition polymerization catalyst, or the reaction product of such combination, and optionally a support.
Additionally according to the present invention there is provided a process for polymerization of one or more ethylenically unsaturated, polymerizable monomers comprising contacting the same, optionally in the presence of an inert aliphatic, alicyclic or aromatic hydrocarbon, with the above catalyst composition or supported catalyst composition.
The foregoing compounds are uniquely adapted for use in activation of a variety of metal complexes, especially Group 4 metal complexes, under standard and atypical olefin polymerization conditions. Because of this fact, the foregoing compounds are capable of forming highly desirable olefin polymers in high efficiency.
All references herein to elements belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1995. Also any reference to the Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. When referred to herein, the teachings of any patent, patent application or publication are hereby incorporated by reference herein.
The catalyst activators of the invention are further characterized in the following manner. A*+a  is desirably chosen to provide overall neutrality to the compound and to not interfere with subsequent catalytic activity. Moreover, the cation may participate in the formation of the active catalyst species, desirably through a proton transfer, oxidation, or ligand abstraction mechanism, or a combination thereof. Additionally, certain cations beneficially improve the solubility of the resulting activator in particular reaction media under use conditions. For example, in the homopolymerization or copolymerization of aliphatic olefins, particularly in the solution phase, an aliphatic diluent is commonly used. Accordingly, cationic species that are relatively soluble in such reaction media, or render the catalyst activator more soluble therein are highly preferred.
Examples of suitable cations include ammonium, sulfonium, phosphonium, oxonium, carbonium, and silylium cations, preferably those containing up to 80 atoms not counting hydrogen, as well as ferrocenium, Ag+, Pb+2, or similar oxidizing cations. As previously mentioned, the cation may also comprise a hydroxyl group or a polar group containing quiescent reactive functionality. In a preferred embodiment, a, b, c and d are all equal to one.
Z* can be any anionic moiety containing two or more Lewis basic sites. Preferably, the Lewis base sites are on different atoms of a polyatomic anionic moiety. Desirably, such Lewis basic sites are relatively sterically accessible to the Lewis acid, J*. Preferably the Lewis basic sites are on nitrogen or carbon atoms. Examples of suitable Z* anions include cyanide, azide, amide and substituted amide, amidinide and substituted amidinide, dicyanamide, imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, tricyanomethide, tetracycanoborate, puride, squarate, 1,2,3-triazolide, substituted 1,2,3-triazolide, 1,2,4-triazolide, substituted 1,2,4-triazolide, pyrimidinide, substituted pyrimidinide, tetraimidazoylborate and substituted tetraimidazoylborate anions, wherein each group, if present, is a halo-, hydrocarbyl-, halohydrocarbyl-, silyl-, (including mono-, di- and tri(hydrocarbyl)silyl-), silylhydrocarbyl-, halocarbyl- or hydroxyl-group, or a polar group containing quiescent reactive functionality, or two such groups together form a saturated or unsaturated ring- or multiple ring-system.
Preferred Z* groups are: imidazolide, 2-nonadecylimidazolide, 2-undecylimidazolide, 2-tridecylimidazolide, 2-pentadecylimidazolide, 2-heptadecylimidazolide, 2-nonadecylimidazolide, 4,5-difluoroimidazolide, 4,5-dichloroimidazolide, 4,5-dibromoimidazolide, 4,5-bis(heptadecyl)imidazolide, 4,5-bis(undecyl)imidazolide, imidazolinide, 2-nonadecylimidazolinide, 2-undecylimidazolinide, 2-tridecylimidazolinide, 2-pentadecylimidazolinide, 2-heptadecylimidazolinide, 2-nonadecylimidazolinide, 4,5-difluoroimidazolinide, 4,5-dichloroimidazolinide, 4,5-dibromoimidazolinide, 4,5-bis(heptadecyl)imidazolinide, 4,5-bis(undecyl)imidazolinide, didecylamide, piperidinide, 4,4-dimethylimidazolinide, tetra-5-pyrimidinylborate, pyrimidinide, 5,6-dichlorobenzimidazolide, 4,5-dicyanoimidazolide, and 5,6-dimethylbenzimidazolide anions, or said Z* groups that are further substituted with a hydroxyl group or a polar group containing quiescent reactive functionality.
Coordinated to the Lewis base sites of the anion are from 2 to 12 Lewis acids, J*, two or more of which may be joined together in a moiety having multiple Lewis acidic functionality. Optionally, said J* group may comprise a hydroxyl group or a polar group containing quiescent reactive functionality, so long as such functionality does not interfere with the Lewis acid functionality of the group. Preferably, from 2 to 4 J* groups having from 3 to 100 atoms not counting hydrogen are present.
More specific examples of the foregoing Lewis acid compounds, J*, correspond to the formula:
wherein:
M* is aluminum, gallium or boron;
R1 and R2 independently each occurrence are hydride, halide, or a hydrocarbyl, halocarbyl, halohydrocarbyl, dialkylamido, alkoxide, or aryloxide group of up to 20 carbons, optionally substituted with a hydroxyl group or a polar group containing quiescent reactive functionality, and
Arf1-Arf2 in combination, independently each occurrence, is a divalent fluoro-substituted aromatic group of from 6 to 20 carbons, optionally substituted with a hydroxyl group or a polar group containing quiescent reactive functionality.
Highly preferred Lewis acids are aluminum or boron compounds corresponding to the formula: AlR13, or BR13, wherein R1 independently each occurrence is selected from hydrocarbyl, halocarbyl, and halohydrocarbyl radicals, or such groups further substituted with a hydroxyl group or a polar group containing quiescent reactive functionality, said R1 having up to 20 carbons. In a more highly preferred embodiment, R1 is a fluorinated C1-20 hydrocarbyl group, most preferably, a fluorinated aryl group, especially, pentafluorophenyl.
Preferred examples of the foregoing Lewis acid groups containing multiple Lewis acid sites are:
By the term xe2x80x9cpolar group containing quiescent reactive functionalityxe2x80x9d is meant an oxygen, nitrogen, sulfur, or phosphorus containing ligand group that is capped or protected and thereby rendered relatively inert to reaction conditions used in the synthesis or use of the present compounds, but wherein the capping or protecting groups may be later removed, if desired, thereby generating a reactive polar functional group, especially a hydroxyl group or metallated derivative thereof. Suitable reactive polar functional groups include hydroxyl, thiol, amine, and phosphine groups, or hydrocarbyl-, alkali metal- or Bronsted acid salt-derivatives thereof. Suitable quiescent reactive functionality includes the trihydrocarbyllsilyl-, trihydrocarbylgermyl-, dihydrocarbylaluminum-, hydrocarbylzinc- or hydrocarbylmagnesium-functionalized derivative of the foregoing polar groups. Particularly preferred polar containing quiescent reactive functional groups are trihydrocarbylsiloxy, trihydrocarbylsiloxy-substituted hydrocarbyl, dihydrocarbylaluminoxy and dihydrocarbylaluminoxy substituted hydrocarbyl groups. Especially preferred are the trialkylsiloxy- or dialkylaluminoxy-derivatives of such polar functional groups, containing from 1 to 6 carbon in each alkyl group. Especially preferred quiescent reactive functional groups are trimethylsiloxy-groups and diethylaluminoxy-groups.
Such polar group containing quiescent reactive functionality is activated by reaction with a metal hydrocarbyl-, metal halocarbyl-, hydrocarbylmetaloxy- or metal halohydrodarbyl-compound under ligand exchange conditions, thereby producing a neutral hydrocarbon, halohydrocarbon, trimethylsilylhydrocarbon, trimethylsilylhalohydrocarbon or trimethylsilylhalocarbon compound as a by-product. The hydroxyl group or polar group containing quiescent reactive functionality may also be employed to react with hydroxyl-, alkylmetal-, hydrocarbylsilyl-, or hydrocarbylsiloxy-functionality of a solid, particulated, support material, optionally after conversion to a metallated or protonated intermediate. This results in tethering or chemically attaching the activator to the surface of the solid, particulated, support material. The resulting substance demonstrates enhanced resistance to loss or removal when exposed to liquids in a polymerization process.
In a preferred embodiment, the foregoing hydroxyl group or polar group containing quiescent reactive functionality is located in the Z* ligand. Examples include hydroxyl, trialkylsiloxy-, trialkylsiloxyalkyl-, trialkylsiloxyaryl-, and dialkylaluminoxyaryl-substituted derivatives of imidazolide, 2-(C1-30hydrocarbyl)imidazolide, 4,5-dihaloimidazolide, 4,5-di(C1-30hydrocarbyl)imidazolide, 4,5-benzylimidazolide, 2-(C1-30hydrocarbyl)-4,5-benzimidazolide, 1,3,4-triazolide, 2-(C1-30hydrocarbyl-1,3,4-triazolide, 1,2,3-triazolide, 4,5-benz-1,2,3-triazolide, imidazolinide, 2-(C1-30hydrocarbyl)imidazolinide, 4,5-dihaloimidazolinide, and 5,6-dimethylbenzimidazolide. Especially preferred examples include hydroxyaryl, trimethylsiloxyaryl-, and dialkylaluminoxyaryl-substituted derivatives of imidazolide, 2-(C1-30alkyl)imidazolide, 4,5-di(C1-30alkyl)imidazolide, 4,5-benzimidazolide, 1,3,4-triazolide, 2-(C1-30alkyl-1,3,4-triazolide, and 1,2,3-triazolide.
Especially suitable expanded anion compounds according to the present invention include the ammonium, phosphonium, sulfonium, oxonium, carbonium, silylium, lead (II), silver or ferrocenium salts of hydroxylphenyl-, trimethylsiloxyphenyl-, and dialkylaluminoxyphenyl-substituted derivatives of: bis(tris(pentafluorophenyl)borane)imidazolide, bis(tris(pentafluorophenyl)borane)-2-undecyl-imidazolide, bis(tris(pentafluorophenyl)borane)imidazolinide, bis(tris(pentafluorophenyl)-borane)-2-undecylimidazolinide, bis(tris(pentafluorophenyl)borane)-4,5-benzimidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide, bis(tris(pentafluorophenyl)borane)1,3,4-triazolide, bis(tris(pentafluorophenyl)borane)-2-undecyl-1,3,4-triazolide, bis(tris(pentafluorophenyl)alumane)imidazolide, bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)alumane)imidazolinide, bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide, bis(tris-(pentafluorophenyl)alumane)-4,5-benzimidazolide, bis(tris(pentafluoro-phenyl)alumane)-4,5-bis(heptadecyl)imidazolide, bis(tris(pentafluorophenyl)alumane)-1,3,4-triazolide, and bis(tris(pentafluorophenyl)alumane)-2-undecyl-1,3,4-triazolide.
Preferred expanded anion compounds are the ammonium salts of the foregoing derivatives, especially those which comprise trihydrocarbyl-substituted ammonium cations, especially trimethylammonium-, triethylammonium-, tripropylammonium-, tri(n-butyl)ammonium-, methyldi(octadecyl)ammonium-, methyldi(tetradecyl)ammonium-, methyl(tetradecyl) (octadecyl)ammonium-, N,N-dimethylanilinium-, N,N-diethylanilinium-, N,N-dimethyl(2,4,6-trimethylanilinium)-, N,N-di(tetradecyl)lanilinium-, N,N-di(tetradecyl)-2,4,6-trimethylanilinium)-, N,N-di(octadecyl)lanilinium-, N,N-di(octadecyl)-2,4,6-trimethylanilinium)-, and methyldicyclohexylammonium-cations, or mixtures thereof.
Most preferred ammonium cation containing salts are those containing trihydrocarbyl-substituted ammonium cations containing one or two C10-C40 alkyl groups, especially methylbis(octadecyl)ammonium- and methylbis(tetradecyl)ammonium-cations. It is further understood that the cation may comprise a mixture of hydrocarbyl groups of differing lengths. For example, the protonated ammonium cation derived from the commercially available long chain amine comprising a mixture of two C14, C16 or C18 alkyl groups and one methyl group. Such amines are available from Witco Corp., under the trade name Kemamine(trademark) T9701, and from Akzo-Nobel under the trade name Armeen(trademark) M2HT.
The foregoing cocatalysts (illustrated by those having substituted-imidazolide, imidazolinide, benzimidazolide, 1,3,4-triazolide, 1,2,3-triazolide, or 4,5-benzyl-1,2,3-triazolide anions containing one or more hydroxyl-, trimethylsiloxy-, trimethylsiloxyalkyl-, or trimethylsiloxyaryl-groups) may be depicted schematically as follows:
wherein:
A*+ is a monovalent cation as previously defined, and preferably is a trihydrocarbyl ammonium cation, containing one or two C10-40 alkyl groups, especially the methylbis(tetradecyl)ammonium- or methylbis(octadecyl)ammonium-cation,
R4, independently each occurrence, is hydrogen or a hydroxyhydrocarbyl, halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl group, (including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms not counting hydrogen, preferably C1-20 alkyl group, or a quiescent reactive group, with the proviso that at least one R4 group contains a hydroxyhydrocarbyl group or a quiescent reactive group, preferably a hydroxyaryl, trialkylsiloxy-, trialkylsiloxyalkyl-, trialkylsiloxyaryl-, or dialkyllaluminoxyaryl-ligand, more preferably a trimethylsiloxy-, trimethylsiloxymethyl-, trimethylsiloxyphenyl-, or diethylaluminoxyphenyl-ligand, and
J*xe2x80x2 is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane).
Examples of the most highly preferred catalyst activators herein include the forgoing trihydrocarbylammonium-, especially, methylbis(tetradecyl)ammonium- or methylbis(octadecyl)ammonium-salts of:
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxybiphenyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-5-(p-hydroxynaphthyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-undecyl-4-(p-hydroxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-heptadecyl-4-(p-hydroxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-4,5-bis(undecyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-4,5-bis(heptadecyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)imidazolinide,
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-1,3,4-triazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-hydroxyphenyl)-4,5-benziimidazolide;
bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-undecyl-4-(p-trimethylsiloxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-heptadecyl-4-(p-trimethylsiloxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-4,5-bis(undecyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-4,5-bis(heptadecyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)imidazolinide,
bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-1,3,4-triazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-trimethylsiloxyphenyl)-4,5-benziimidazolide;
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxybiphenyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-5-(p-diethylaluminoxynaphthyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-undecyl-4-(p-diethylaluminoxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-heptadecyl-4-(p-diethylaluminoxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-4,5-bis(undecyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-4,5-bis(heptadecyl)imidazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)imidazolinide,
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-1,3,4-triazolide,
bis(tris(pentafluorophenyl)borane)-2-(p-diethylaluminoxyphenyl)-4,5-benziimidazolide;
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-undecyl-4-(p-hydroxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-heptadecyl-4-(p-hydroxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-4,5-bis(undecyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-4,5-bis(heptadecyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)imidazolinide,
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-1,3,4-triazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-hydroxyphenyl)-4,5-benziimidazolide;
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-undecyl-4-(p-trimethylsiloxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-heptadecyl-4-(p-trimethylsiloxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-4,5-bis(undecyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-4,5-bis(heptadecyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)imidazolinide,
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-1,3,4-triazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-trimethylsiloxyphenyl)-4,5-benziimidazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-undecyl-4-(p-diethylaluminoxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-heptadecyl-4-(p-diethylaluminoxyphenyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-4,5-bis(undecyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-4,5-bis(heptadecyl)imidazolide,
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)imidazolinide,
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-1,3,4-triazolide, and
bis(tris(pentafluorophenyl)alumane)-2-(p-diethylaluminoxyphenyl)-4,5-benziimidazolide.
The compounds may be prepared by a condensation reaction between the alkali metal salt of the anion, Z*, and a Lewis acid, J*, preferably under phase transfer conditions, using for example a crown ether to solubilize the alkali metal salt if necessary, followed by a metathesis reaction with the corresponding halide salt of the cation, A*+a. Certain of the cocatalysts are also amenable to preparation via a one step, single reactor process. For example, the ammonium- or phosphonium-substituted hydroxyl group or quiescent reactive group-substituted imidiazolide salts can be prepared by contacting the Lewis acid, J*, or its Lewis base adduct, such as an etherate, with the neutral compound corresponding to the anion, Z*. Both reactants are desirably relatively lipophilic, such that the reaction can be performed in non-polar solvents. Addition of the free base corresponding to the cation, A*+a, results in formation of the charge separated species, which may be recovered from the reaction mixture by devolatilization or used without further purification.
The corresponding reactive hydroxyl-, thiol, amine, or phosphine containing compound (or its metal or ammonium salt derivative) may be generated or produced in situ by reaction of the quiescent reactive groups of the present compounds with any suitable reactant, such as a hydrocarbon, a metal fluoride, an ammonium fluoride, or an acid, thereby removing the capping or protecting group(s).
Due to the presence of the hydroxyl group or quiescent reactive functionality in the compounds of the present invention, or reactive derivatives thereof, the present compounds may be readily attached to a reactive substrate, such as a particulated solid containing reactive hydrocarbyl groups, especially hydrocarbylmetal- or hydrocarbylmetalloid-functionality. Examples include alumina, silica, aluminosilicates, and aluminum magnesium silicate materials, containing reactive hydroxyl- or hydrocarbyl-functionality, and such materials treated with any substance to impart reactive metal-hydrocarbyl or metalloid-hydrocarbyl functionality. Examples of such treating substances include trihydrocarbyl aluminum compounds, chlorosilane compounds, and mono- or di-hydrocarbylsilane compounds that react with a portion or all of reactive surface hydroxyl functionality of the substrate to form a xe2x80x9ccappedxe2x80x9d derivative. This technique is known in the art and disclosed for example in U.S. Pat. No. 6,087,293.
Suitable catalysts for use in combination with the foregoing cocatalysts include any compound or complex of a metal of Groups 3-10 of the Periodic Table of the Elements capable of being activated to polymerize ethylenically unsaturated compounds by the present activators. Examples include Group 10 diimine derivatives corresponding to the formula:
wherein
M* is Ni(II) or Pd(II);
K is halo, hydrocarbyl, or hydrocarbyloxy;
and the two nitrogen atoms are linked by a bridging system.
Such catalysts have been previously disclosed in J. Am. Chem. Soc., 118, 267-268 (1996), J. Am. Chem. Soc., 117, 6414-6415 (1995), and Organometallics, 16, 1514-1516, (1997).
Additional catalysts include derivatives of Group 3, 4, or Lanthanide metals which are in the +2, +3, or +4 formal oxidation state. Preferred compounds include metal complexes containing from 1 to 3 xcfx80-bonded anionic or neutral ligand groups, which may be cyclic or non-cyclic delocalized xcfx80-bonded anionic ligand groups. Exemplary of such xcfx80-bonded anionic ligand groups are conjugated or nonconjugated, cyclic or non-cyclic dienyl groups, allyl groups, boratabenzene groups, phosphole, and arene groups. By the term xe2x80x9cxcfx80-bondedxe2x80x9d is meant that the ligand group is bonded to the transition metal by a sharing of electrons from a partially delocalized xcfx80-bond.
Each atom in the delocalized xcfx80-bonded group may independently be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements, and such hydrocarbyl- or hydrocarbyl-substituted metalloid radicals further substituted with a Group 15 or 16 hetero atom containing moiety. Included within the term xe2x80x9chydrocarbylxe2x80x9d are C1-20 straight, branched and cyclic alkyl radicals, C6-20 aromatic radicals, C7-20 alkyl-substituted aromatic radicals, and C7-20 aryl-substituted alkyl radicals. In addition two or more such radicals may together form a fused ring system, including partially or fully hydrogenated fused ring systems, or they may form a metallocycle with the metal. Suitable hydrocarbyl-substituted organometalloid radicals include mono-, di- and tri-substituted organometalloid radicals of Group 14 elements wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples of suitable hydrocarbyl-substituted organometalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups. Examples of Group 15 or 16 hetero atom containing moieties include amine, phosphine, ether or thioether moieties or divalent derivatives thereof, e.g. amide, phosphide, ether or thioether groups bonded to the transition metal or Lanthanide metal, and bonded to the hydrocarbyl group or to the hydrocarbyl-substituted metalloid containing group.
Examples of suitable anionic, delocalized xcfx80-bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, phosphole, and boratabenzene groups, as well as hydrocarbyl-silyl- (including mono-, di-, or tri(hydrocarbyl)silyl) substituted derivatives thereof. Preferred anionic, delocalized xcfx80-bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethyl(trimethylsilyl)-cyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, and tetrahydroindenyl.
The boratabenzenes are anionic ligands that are boron containing analogues to benzene. They are previously known in the art having been described by G. Herberich, et al., in Organometallics, 14,1, 471-480 (1995). Preferred boratabenzenes correspond to the formula:
wherein Rxe2x80x3 is selected from the group consisting of hydrocarbyl, silyl, N,N-dihydrocarbylamino, or germyl, said Rxe2x80x3 having up to 20 non-hydrogen atoms. In complexes involving divalent derivatives of such delocalized xcfx80-bonded groups one atom thereof is bonded by means of a covalent bond or a covalently bonded divalent group to another atom of the complex thereby forming a bridged system.
Phospholes are anionic ligands that are phosphorus containing analogues to a cyclopentadienyl group. They are previously known in the art having been described by WO 98/50392, and elsewhere. Preferred phosphole ligands correspond to the formula:
wherein Rxe2x80x3 is selected from the group consisting of hydrocarbyl, silyl, N,N-dihydrocarbylamino, or germyl, said Rxe2x80x3 having up to 20 non-hydrogen atoms, and optionally one or more Rxe2x80x3 groups may be bonded together forming a multicyclic fused ring system, or form a bridging group connected to the metal. In complexes involving divalent derivatives of such delocalized xcfx80-bonded groups one atom thereof is bonded by means of a covalent bond or a covalently bonded divalent group to another atom of the complex thereby forming a bridged system.
Phosphinimine/cyclopentadienyl complexes are disclosed in EP-A-890581 and correspond to the formula
[(R***)3xe2x80x94Pxe2x95x90N]bM**(Cp)(L1)3-b,
wherein:
R*** is a monovalent ligand, illustrated by hydrogen, halogen, or hydrocarbyl, or two R*** groups together form a divalent ligand,
M** is a Group 4 metal,
Cp is cyclopentadienyl, or similar delocalized xcfx80-bonded group,
L1 is a monovalent ligand group, illustrated by hydrogen, halogen or hydrocarbyl,
b is a number from 1 to 3; and
n is 1 or 2.
A suitable class of catalysts are transition metal complexes corresponding to the formula:
LplMXmXxe2x80x2nXxe2x80x3p, or a dimer thereof
wherein:
Lp is an anionic, delocalized, xcfx80-bonded group that is bound to M, containing up to 50 non-hydrogen atoms, optionally two Lp groups may be joined together forming a bridged structure, and further optionally one Lp may be bound to X;
M is a metal of Group 4 of the Periodic Table of the Elements in the +2, +3 or +4 formal oxidation state;
X is an optional, divalent group of up to 50 non-hydrogen atoms that together with Lp forms a metallocycle with M;
Xxe2x80x2 is an optional neutral ligand having up to 20 non-hydrogen atoms;
Xxe2x80x3 each occurrence is a monovalent, anionic moiety having up to 40 non-hydrogen atoms, optionally, two Xxe2x80x3 groups may be covalently bound together forming a divalent dianionic moiety having both valences bound to M, or, optionally 2 Xxe2x80x3 groups may be covalently bound together to form a neutral, conjugated or nonconjugated diene that is xcfx80-bonded to M (whereupon M is in the +2 oxidation state), or further optionally one or more Xxe2x80x3 and one or more Xxe2x80x2 groups may be bonded together thereby forming a moiety that is both covalently bound to M and coordinated thereto by means of Lewis base functionality;
l is 0, 1 or 2;
m is 0 or 1;
n is a number from 0 to 3;
p is an integer from 0 to 3; and
the sum, l+m+p, is equal to the formal oxidation state of M, except when 2 Xxe2x80x3 groups together form a neutral conjugated or non-conjugated diene that is xcfx80-bonded to M, in which case the sum l+m is equal to the formal oxidation state of M.
Preferred complexes include those containing either one or two Lp groups. The latter complexes include those containing a bridging group linking the two Lp groups. Preferred bridging groups are those corresponding to the formula (ER*2)X, B(NR**2), or B(NR**2)2, wherein E is silicon, germanium, tin, or carbon, R* independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof, said R* having up to 30 carbon or silicon atoms, R** independently each occurrence is a group selected from silyl, hydrocarbyl, and combinations thereof, said R** having up to 30 carbon or silicon atoms, and x is 1 to 8. Preferably, R* independently each occurrence is methyl, ethyl, propyl, benzyl, butyl, phenyl, methoxy, ethoxy, or phenoxy, and R** is methyl, ethyl, propyl, benzyl or butyl.
Examples of the complexes containing two Lp groups are compounds corresponding to the formula:
wherein:
M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the +2 or +4 formal oxidation state;
R3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together form a divalent derivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system, and
Xxe2x80x3 independently each occurrence is an anionic ligand group of up to 40 non-hydrogen atoms, or two Xxe2x80x3 groups together form a divalent anionic ligand group of up to 40 non-hydrogen atoms or together are a conjugated diene having from 4 to 30 non-hydrogen atoms forming a xcfx80-complex with M, whereupon M is in the +2 formal oxidation state, and
R*, R**, E and x are as previously defined, preferably (ER*2)x is dimethylsilandiyl or ethylene, and BNR**2 is di(isopropyl)aminoborandiyl.
The foregoing metal complexes are especially suited for the preparation of polymers having stereoregular molecular structure. In such capacity it is preferred that the complex possesses Cs symmetry or possesses a chiral, stereorigid structure. Examples of the first type are compounds possessing different delocalized xcfx80-bonded systems, such as one cyclopentadienyl group and one fluorenyl group. Similar systems based on Ti(IV) or Zr(IV) were disclosed for preparation of syndiotactic olefin polymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980). Examples of chiral structures include rac bis-indenyl complexes. Similar systems based on Ti(IV) or Zr(IV) were disclosed for preparation of isotactic olefin polymers in Wild et al., J. Organomet. Chem., 232, 233-47, (1982).
Exemplary bridged ligands containing two xcfx80-bonded groups are: dimethylbis(cyclopentadienyl)silane, dimethylbis(tetramethylcyclopentadienyl)silane, dimethylbis(2-ethylcyclopentadien-1-yl)silane, dimethylbis(2-t-butylcyclopentadien-1-yl)silane, 2,2-bis(tetramethylcyclopentadienyl)propane, dimethylbis(inden-1-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane, dimethylbis(fluoren-1-yl)silane, dimethylbis(tetrahydrofluoren-1-yl)silane, dimethylbis(2-methyl-4-phenylinden-1-yl)silane, dimethylbis(2-methylinden-1-yl)silane, di(isopropyl)aminobis(cyclopentadien-1-yl)borandiyl, di(isopropyl)aminobis(2-methyl-4-phenylinden-1-yl)-borandiyl, di(isopropyl)aminobis(2-methylinden-1-yl)borandiyl, dimethyl(cyclopentadienyl)(fluoren-1-yl)silane, dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane, dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane, (1,1,2,2-tetramethy)-1,2-bis(cyclopentadienyl)disilane, (1,2-bis(cyclopentadienyl)ethane, and dimethyl(cyclopentadienyl)-1-(fluoren-1-yl)methane.
Preferred Xxe2x80x3 groups are selected from hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl and aminohydrocarbyl groups, or two Xxe2x80x3 groups together form a divalent derivative of a conjugated diene or else together they form a neutral, xcfx80-bonded, conjugated diene. Most preferred Xxe2x80x3 groups are C1-20 hydrocarbyl groups.
Complexes containing two Lp groups including bridged complexes suitable for use in the present invention include:
bis(cyclopentadienyl)zirconiumdimethyl,
bis(cyclopentadienyl)zirconium dibenzyl,
bis(cyclopentadienyl)zirconium methyl benzyl,
bis(cyclopentadienyl)zirconium methyl phenyl,
bis(cyclopentadienyl)zirconiumdiphenyl,
bis(cyclopentadienyl)titanium-allyl,
bis(cyclopentadienyl)zirconiummethylmethoxide,
bis(cyclopentadienyl)zirconiummethylchloride,
bis(pentamethylcyclopentadienyl)zirconiumdimethyl,
bis(pentamethylcyclopentadienyl)titaniumdimethyl,
bis(indenyl)zirconiumdimethyl,
indenylfluorenylzirconiumdimethyl,
bis(indenyl)zirconiummethyl(2-(dimethylamino)benzyl),
bis(indenyl)zirconiummethyltrimethylsilyl,
bis(tetrahydroindenyl)zirconiummethyltrimethylsilyl,
bis(pentamethylcyclopentadienyl)zirconiummethylbenzyl,
bis(pentamethylcyclopentadienyl)zirconiumdibenzyl,
bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide,
bis(pentamethylcyclopentadienyl)zirconiummethylchloride,
bis(methylethylcyclopentadienyl)zirconiumdimethyl,
bis(butylcyclopentadienyl)zirconiumdibenzyl,
bis(t-butylcyclopentadienyl)zirconiumdimethyl,
bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl,
bis(methylpropylcyclopentadienyl)zirconiumdibenzyl,
bis(trimethylsilylcyclopentadienyl)zirconiumdibenzyl,
dimethylsilyl-bis(cyclopentadienyl)zirconiumdimethyl,
dimethylsilyl-bis(tetramethylcyclopentadienyl)titanium (III) allyl
dimethylsilyl-bis(t-butylcyclopentadienyl)zirconiumdibenzyl,
dimethylsilyl-bis(n-butylcyclopentadienyl)zirconium bis(trimethylsilyl),
(methylene-bis(tetramethylcyclopentadienyl)titanium(III) 2-(dimethylamino)benzyl,
(methylene-bis(n-butylcyclopentadienyl)titanium(III) 2-(dimethylamino)benzyl,
dimethylsilyl-bis(indenyl)zirconiumbenzylchloride,
dimethylsilyl-bis(2-methylindenyl)zirconiumdimethyl,
dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdimethyl,
dimethylsilyl-bis(2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene,
dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium (II) 1,4-diphenyl-1,3-butadiene, dimethylsilyl-bis(tetrahydroindenyl)zirconium (II) 1,4-diphenyl-1,3-butadiene,
di(isopropylamino)borandiylbis(2-methyl-4-phenylindenyl)zirconium dimethyl,
dimethylsilyl-bis(tetrahydrofluorenyl)zirconium bis(trimethylsilyl),
(isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl, and
dimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconium dimethyl.
A further class of metal complexes utilized in the present invention corresponds to the preceding formula
LplMXmXxe2x80x2nXxe2x80x3p,
or a dimer thereof, wherein X is a divalent group of up to 50 non-hydrogen atoms that together with Lp forms a metallocycle with M.
Preferred divalent X groups include groups containing up to 30 non-hydrogen atoms comprising at least one atom that is oxygen, sulfur, boron or a member of Group 14 of the Periodic Table of the Elements directly attached to the delocalized =-bonded group, and a different atom, selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur that is covalently bonded to M.
A preferred class of such Group 4 metal coordination complexes used according to the present invention corresponds to the formula:
wherein:
M is titanium or zirconium, preferably titanium in the +2, +3, or +4 formal oxidation state;
R3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together form a divalent derivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system,
each Xxe2x80x3 is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, said group having up to 20 non-hydrogen atoms, or two Xxe2x80x3 groups together form a neutral C5-30 conjugated diene or a divalent derivative thereof;
Y is xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94NR*xe2x80x94, xe2x80x94PR*xe2x80x94; and
Z is SiR*2, CR*2, SiR*2SiR*2, CR*2CR*2, CR*xe2x95x90CR*, CR*2SiR*2, GeR*2, or B(NR**2) wherein R* and R** are as previously defined.
Illustrative Group 4 metal complexes of the latter formula that may be employed in the practice of the present invention include:
cyclopentadienyltitaniumtrimethyl,
indenyltitaniumtrimethyl,
octahydrofluorenyltitaniumtrimethyl,
tetrahydroindenyltitaniumtrimethyl,
tetrahydrofluorenyltitaniumtrimethyl,
(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-xcex7-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,
(tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-xcex7-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethylsilanetitanium dibenzyl,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethylsilanetitanium dimethyl,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)-1,2-ethanediyltitanium dimethyl,
(tert-butylamido)(tetramethyl-xcex75-indenyl)dimethylsilanetitanium dimethyl,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethylsilane titanium (III) 2-(dimethylamino)benzyl;
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethylsilanetitanium (III) allyl,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethylsilanetitanium (III) 2,4-dimethylpentadienyl,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,
(tert-butylamido)(tetramethyl-xcex75-cylopentadienyl)dimethylsilanetitanium (II) 1,3-pentadiene,
(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (ii) 1,4-diphenyl-1,3-butadiene,
(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II) 2,4-hexadiene,
(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) 2,3-dimethyl-1,3-butadiene,
(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) isoprene,
(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) 1,3-butadiene,
(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) 2,3-dimethyl-1,3-butadiene,
(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) isoprene
(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) dimethyl
(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) dibenzyl
(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) 1,3-butadiene,
(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II), 1,3-pentadiene,
(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,
(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II) 1,3-pentadiene,
(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) dimethyl,
(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) dibenzyl,
(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II), 1,4-diphenyl-1,3-butadiene,
(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II) 1,3-pentadiene,
(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II) 2,4-hexadiene,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethyl-silanetitanium (IV) 1,3-butadiene,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethylsilanetitanium (IV) 2,3-dimethyl-1,3-butadiene,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethylsilanetitanium (IV) isoprene,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethyl-silanetitanium (II) 1,4-dibenzyl-1,3-butadiene,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethylsilanetitanium (II) 2,4-hexadiene,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl)dimethyl-silanetitanium (II) 3-methyl-1,3-pentadiene,
(tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanetitaniumdimethyl,
(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-xcex7-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,
(tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-xcex7-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl methylphenylsilanetitanium (IV) dimethyl,
(tert-butylamido)(tetramethyl-xcex75-cyclopentadienyl methylphenylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,
1-(tert-butylamido)-2-(tetramethyl-xcex75-cyclopentadienyl)ethanediyltitanium (IV) dimethyl,
1-(tert-butylamido)-2-(tetramethyl-xcex75-cyclopentadienyl)ethanediyl titanium (II) 1,4-diphenyl-1,3-butadiene,
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV) 2,3-dimethyl-1,3-butadiene,
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV) isoprene
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV) dimethyl
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV) dibenzyl
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV) 1,3-butadiene,
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (II) 1,3-pentadiene,
(tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene, and
(tert-butylamido)(3-N-pyrrolidinylinden-1-yl)dimethylsilanetitanium (IV) dimethyl.
Other catalysts, especially catalysts containing other Group 4 metals, will, of course, be apparent to those skilled in the art. Most highly preferred metal complexes for use herein are the following metal complexes:
(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium dimethyl,
(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene,
(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (II) 1,4 diphenyl-1,3-butadiene,
(cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium dimethyl, cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (II) 1,4 diphenyl-1,3-butadiene,
(cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium dimethyl, (cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene,
(cyclododecylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (II) 1,4 diphenyl-1,3-butadiene,
(t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium dimethyl,
(t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium (II) 1,3-pentadiene,
(t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium (II) 1,4 diphenyl-1,3-butadiene,
(cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium dimethyl, cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium (II) 1,3-pentadiene, cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
(cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium dimethyl,
(cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II) 1,3-pentadiene,
(cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II) 1,4diphenyl-1,3-butadiene,
(t-butylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium dimethyl,
(t-butylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium(II) 1,3-pentadiene,
(t-butylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
(cyclohexylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium dimethyl, cyclohexylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium(II) 1,3-pentadiene, cyclohexylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
(cyclododecylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium dimethyl,
(cyclododecylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium(II) 1,3-pentadiene,
(cyclododecylamido)dimethyl(3,4-(cyclopenta(I)phenanthren-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium dimethyl,
(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1,3-pentadiene,
(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
(cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium dimethyl, cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1,3-pentadiene, cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II)1,4 diphenyl-1,3-butadiene,
(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium dimethyl,
(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1,3-pentadiene,
(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium dimethyl,
(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium (II) 1,3-pentadiene,
(t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium (II) 1,4 diphenyl-1,3-butadiene,
(cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium dimethyl, cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium((II) 1,3-pentadiene, cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium dimethyl,
(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1,3-pentadiene,
(cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium dimethyl,
(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II) 1,3-pentadiene,
(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
(cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium dimethyl, cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II) 1,3-pentadiene, cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium dimethyl,
(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II) 1,3-pentadiene,
(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium dimethyl,
(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium (II)1,3-pentadiene,
(t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium (II) 1,4 diphenyl-1,3-butadiene,
(cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium dimethyl, cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II) 1,3-pentadiene, cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium dimethyl,
(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II) 1,3-pentadiene,
(cyclododecylamido)dimethyl(3-(1-pyrrolidinyl)inden-1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene,
1,2-ethanebis(inden-1-yl)zirconium dimethyl,
1,2-ethanebis(inden-1-yl)zirconium(II) 1,3-pentadiene, 1,2-ethanebis(inden-1-yl)zirconium(II) 1,4 diphenyl-1,3-butadiene,
1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium dimethyl,
1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium(II) 1,3-pentadiene,
1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium(II) 1,4 diphenyl-1,3-butadiene,
dimethylsilanebis(inden-1-yl)zirconium dimethyl,
dimethylsilanebis(inden-1-yl)zirconium(II) 1,3-pentadiene,
dimethylsilanebis(inden-1-yl)zirconium(II) 1,4 diphenyl-1,3-butadiene,
dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium dimethyl,
dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium(II) 1,3-pentadiene, and
dimethylsilanebis(2-methyl-4-phenylinden-1-yl)zirconium(II) 1,4 diphenyl-1,3-butadiene.
The expanded anion cocatalysts of the invention may also be used in combination with an oligomeric or polymeric alumoxane compound, a tri(hydrocarbyl)aluminum compound, a di(hydrocarbyl) (hydrocarbyloxy)aluminum compound, a di(hydrocarbyl)(dihydrocarbyl-amido)aluminum compound, a bis(dihydrocarbyl-amido) (hydrocarbyl)aluminum compound, a di(hydrocarbyl)amido(disilyl)aluminum compound, a di(hydrocarbyl)amido(hydrocarbyl)(silyl)aluminum compound, a bis(dihydrocarbylamido)(silyl)aluminum compound, or a mixture of the foregoing compounds, having from 1 to 20 non-hydrogen atoms in each hydrocarbyl, hydrocarbyloxy, or silyl group, if desired. These aluminum compounds are usefully employed for their beneficial ability to scavenge impurities such as oxygen, water, and aldehydes from the polymerization mixture as well as to react with the hydroxyl group or quiescent reactive functionality of the compounds or the reactive derivatives thereof.
Preferred aluminum compounds include C1-20 trialkyl aluminum compounds, especially those wherein the alkyl groups are ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl, dialkyl(aryloxy)aluminum compounds containing from 1-6 carbons in the alkyl group and from 6 to 18 carbons in the aryl group (especially (3,5-di(t-butyl)-4-methylphenoxy)diisobutylaluminum), methylalumoxane, modified methalumoxane, especially isobutyl modified alumoxane, and tri(ethylaluminum)-, tris(pentafluorophenyl)borane-, or tris(pentafluorophenyl)aluminum-modified alumoxanes or supported derivatives thereof. (The latter compositions are previously known, having been disclosed in WO99/15534. Additional species include mixtures of aluminum containing Lewis acids as disclosed in pending U.S. patent applications Ser. Nos. 09/330,673 and 09/330,675. The molar ratio of activator to aluminum compound is preferably from 1:10,000 to 1000:1, more preferably from 1:5000 to 100:1, most preferably from 1:100 to 100:1.
The cocatalysts of the present invention are capable of activating a wide variety of metal complexes. Moreover, the cocatalysts can be optimized in their ability to activate different metal complexes through combination of anions, Z*, having Lewis base sites of varying base strength, and Lewis acids, J*, having varying acidity. Thus, use of derivatives of weakly basic anions such as dicyanamide, 1,2,4-triazolide and 4,5-dichloroimidazolide give expanded anion salts which are less active cocatalysts, all other variables being the same, than do derivatives of moderately basic anions, such as cyanide, azide, benzotriazolide, benzimidazolide and tetraimidazoylborate, which in turn give less active cocatalalysts than derivatives of even more basic anions, such as 4,4-dimethylimidazolinide, imidazolide, 5,6-dimethylbenzimidazolide and 2-undecylimidazolide.
The equivalent ratio of catalyst/cocatalyst (calculated based on quantity of metal in the catalyst and anionic charges on the cocatalyst) employed preferably ranges from 1:10 to 10:1, more preferably from 1:5 to 2:1, most preferably from 1:4 to 1:1. Mixtures of the activating cocatalysts of the present invention may also be employed if desired.
Suitable addition polymerizable monomers include ethylenically unsaturated monomers, acetylenic compounds, conjugated or non-conjugated dienes, and polyenes. Preferred monomers include olefins, for examples alpha-olefins having from 2 to 20,000, preferably from 2 to 20, more preferably from 2 to 8 carbon atoms and combinations of two or more of such alpha-olefins. Particularly suitable alpha-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, or combinations thereof, as well as long chain vinyl terminated oligomeric or polymeric reaction products formed during the polymerization, and C10-30 xcex1-olefins specifically added to the reaction mixture in order to produce relatively long chain branches in the resulting polymers. Preferably, the alpha-olefins are ethylene, propene, 1-butene, 4-methyl-pentene-1,1-hexene, 1-octene, and combinations of ethylene and/or propene with one or more of such other alpha-olefins. Other preferred monomers include styrene, halo- or alkyl substituted styrenes, vinylbenzocyclobutene, 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, and 1,7-octadiene. Mixtures of the above-mentioned monomers may also be employed.
In general, the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions. Suspension, solution, slurry, gas phase or high pressure, whether employed in batch or continuous form or other process conditions, may be employed if desired. Examples of such well known polymerization processes are depicted in WO 88/02009, U.S. Pat. Nos. 5,084,534, 5,405,922, 4,588,790, 5,032,652, 4,543,399, 4,564,647, 4,522,987, and elsewhere. Preferred polymerization temperatures are from 0-250xc2x0 C. Preferred polymerization pressures are from atmospheric to 3000 atmospheres.
Suitable processing conditions include solution polymerization, more preferably continuous solution polymerization processes, conducted in the presence of an aliphatic or alicyclic liquid diluent, preferably using the unsupported, quiescent reactive functionality containing compounds. By the term xe2x80x9ccontinuous polymerizationxe2x80x9d is meant that at least the products of the polymerization are continuously removed from the reaction mixture, such as for example by devolatilization of a portion of the reaction mixture. Preferably one or more reactants are also continuously added to the polymerization mixture during the polymerization. Examples of suitable aliphatic or alicyclic liquid diluents include straight and branched-chain C4-12 hydrocarbons and mixtures thereof; alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; and perfluorinated hydrocarbons such as perfluorinated C4-10 alkanes, and the like. Suitable diluents also include aromatic hydrocarbons (particularly for use with aromatic xcex1-olefins such as styrene or ring alkyl-substituted styrenes) including toluene, ethylbenzene or xylene, as well as liquid olefins (which may act as monomers or comonomers) including ethylene, propylene, butadiene, cyclopentene, 1-hexene, 3-methyl-1pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene, allylbenzene, vinyltoluene (including all isomers alone or in admixture), and the like. Mixtures of the foregoing are also suitable. The foregoing diluents may also be advantageously employed during the synthesis of the metal complexes and catalyst activators of the present invention.
In most polymerization reactions the molar ratio of catalyst:polymerizable compounds employed is from 10xe2x88x9212:1 to 0.1:1, more preferably from 10xe2x88x9212:1 to 10xe2x88x925:1.
The catalyst composition of the invention may also be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties. An example of such a process is disclosed in WO 94/00500.
Molecular weight control agents can be used in combination with the present cocatalysts. Examples of such molecular weight control agents include hydrogen, trialkyl aluminum compounds or other known chain transfer agents. A particular benefit of the use of the present cocatalysts is the ability (depending on reaction conditions) to produce narrow molecular weight distribution xcex1-olefin homopolymers and copolymers in greatly improved catalyst efficiencies. Preferred polymers have Mw/Mn of less than 2.5, more preferably less than 2.3. Such narrow molecular weight distribution polymer products are highly desirable due to improved tensile strength properties.
The catalyst composition of the present invention can also be employed to advantage in the gas phase polymerization and copolymerization of olefins. Gas phase processes for the polymerization of olefins, especially the homopolymerization and copolymerization of ethylene and propylene, and the copolymerization of ethylene with higher alpha olefins such as, for example, 1-butene, 1-hexene, 4-methyl-1-pentene are well known in the art. Such processes are used commercially on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene.
The gas phase process employed can be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone. Preferred is the process wherein the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported above a perforated plate, the fluidisation grid, by a flow of fluidisation gas.
The gas employed to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. The hot gases emerge from the top of the reactor, normally via a tranquilization zone, also known as a velocity reduction zone, having a wider diameter than the fluidized bed and wherein fine particles entrained in the gas stream have an opportunity to gravitate back into the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the hot gas stream. The gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization.
A preferred method of cooling of the bed, in addition to the cooling provided by the cooled recycle gas, is to feed a volatile liquid to the bed to provide an evaporative cooling effect. The volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having about 3 to about 8, preferably 4 to 6, carbon atoms. In the case that the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid this can be suitably be fed to the bed to provide an evaporative cooling effect. Examples of olefin monomers which can be employed in this manner are olefins containing from about 3 to about eight, preferably from 3 to six carbon atoms. The volatile liquid evaporates in the hot fluidized bed to form gas which mixes with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed. The evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop. The recycle gas is cooled in the heat exchanger and, if the temperature to which the gas is cooled is below the dew point, liquid will precipitate from the gas. This liquid is desirably recycled continuously to the fluidized bed. It is possible to recycle the precipitated liquid to the bed as liquid droplets carried in the recycle gas stream, as described, for example, in EP-A-89691, U.S. Pat. No. 4,543,399, WO 94/25495 and U.S. Pat. No. 5,352,749. A particularly preferred method of recycling the liquid to the bed is to separate the liquid from the recycle gas stream and to reinject this liquid directly into the bed, preferably using a method which generates fine droplets of the liquid within the bed. This type of process is described in WO 94/28032.
The polymerization reaction occurring in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst. Such catalyst can be supported on an inorganic or organic support material if desired. The catalyst can also be subjected to a prepolymerization step, for example, by polymerizing a small quantity of olefin monomer in a liquid inert diluent, to provide a catalyst composite comprising catalyst particles embedded in olefin polymer particles.
The polymer is produced directly in the fluidized bed by catalyzed (co)polymerization of the monomer(s) on the fluidized particles of catalyst, supported catalyst or prepolymer within the bed. Start-up of the polymerization reaction is achieved using a bed of preformed polymer particles, which, preferably, is similar to the target polyolefin, and conditioning the bed by drying with inert gas or nitrogen prior to introducing the catalyst, the monomer(s) and any other gases which it is desired to have in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating in gas phase condensing mode. The produced polymer is discharged continuously or discontinuously from the fluidized bed as desired, optionally exposed to a catalyst kill and optionally pelletized.
Slurry polymerization conditions and supported catalyst preparation techniques for use therein are well known from the published literature. Generally such catalysts are prepared by the same techniques as are employed for making supported catalysts used in gas phase polymerizations. Slurry polymerization conditions generally encompass polymerization of a C2-20 olefin, diolefin, cycloolefin, or mixture thereof in an aliphatic solvent at a temperature below that at which the polymer is readily soluble in the presence of a supported catalyst. Slurry phase processes particularly suited for the polymerization of C2-6 olefins, especially the homopolymerization and copolymerization of ethylene and propylene, and the copolymerization of ethylene with C3-8 xcex1-olefins such as, for example, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are well known in the art. Such processes are used commercially on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene, especially isotactic polypropylene.

Expanded anionic compounds comprising hydroxyl or quiescent reactive functionality and catalyst activators therefrom

Abstract: wherein:

Abstract: j is a number from 2 to 12 and


A lift and tilt chair including both motorized lift capability and motorized tilting capability A hydraulic lift cylinder is provided and operates in conjunction with a motorized tilting system. A seat support is provided having rollers affixed thereto for providing the tilting motion and having the lift cylinder attached thereto for allowing raising and lowering of a patient seated within the chair.

The present invention generally relates to medical chairs and, more specifically, to chairs that may be moved by a medical professional to place a patient in a desired position.
Many different types of chairs have been developed in the medical field for placing patients in a desired position for treatment or diagnosis. These include dental chairs and ophthalmological chairs. One such chair is disclosed in U.S. Pat. No. 5,467,002, assigned to the assignee of the present invention, the disclosure of which is hereby fully incorporated by reference herein. The chair disclosed in this patent has the ability to raise and lower a patient seated within the chair and also the ability to recline the patient and raise the patient""s feet by way of a pivoting backrest, leg rest and footrest. Often, it is desirable to simply tilt the patient back while leaving the patient in essentially the same seated position. Such chairs are typically referred to as xe2x80x9ctilt chairsxe2x80x9d. Various tilt chairs have been proposed in the past, however, no chair to date has adequately and efficiently allowed a medical professional to both tilt a patient into position and raise or lower the patient during or after diagnosis or treatment.
For these and other reasons, it would be desirable to provide a tilt chair which is cost efficient in design, yet may be used by a medical professional to both tilt a patient automatically into position and raise or lower that patient into the ultimately desired position.
To these ends, the present invention provides a medical chair having a patient support generally affixed to a base by a lifting and tilting mechanism. The lifting and tilting mechanism generally comprises a seat support having four rollers mounted thereon and contained within slots respectively contained in a pair of support rails affixed to the back of the patient support. A pair of rollers is mounted to the front of the seat support and a pair is mounted to the rear thereof. The slots are curved to define the tilting path of the chair. The lifting and tilting mechanism further includes a lifting cylinder rigidly affixed to the seat support between the front and rear pairs of rollers. This lifting cylinder is connected to a motorized hydraulic pump contained in the base of the chair. An actuator is affixed between the patient support and the seat support for moving the patient support relative to the seat support by movement of the rails along the front and rear pairs of rollers. Significantly, the front and rear pairs of rollers are mounted to the seat support in generally the same horizontal plane for stability, ease of manufacture and proper movement of the rollers within the guide slots.
It will be appreciated that the invention provides a chair that may have a single foot control for use by a medical professional to provide powered movement both in a tilting manner and a vertical direction to adjust the position of a patient undergoing diagnosis or treatment. The invention further provides such advantage in a cost efficient manner due to the integrated design of the lifting and tilting mechanism. Additional advantages and objects of the invention will become more readily apparent to those of ordinary skill upon review of the following detailed description of the preferred embodiment taken in conjunction with the accompanying drawings.

Examination chair with lifting and tilting mechanism


A pill sorter with bag sealer designed for the dispensation and storage of easily transportable packages of medication. The pill sorter has one or more independent chambers that can store pills or other medication. The pill sorter dispenses medication through a funneled lid, allowing the user to dispense a single chamber's medication into a plastic bag. The plastic bag is placed into a bag sealer having an activation button, light-emitting diode (LED), battery, microprocessor, and sealing element. The activation time of the sealing element is adjusted by the microprocessor based upon the measured level of charge present in the battery, providing a one-touch sealing solution to the user. The sealing element seals the plastic bag, which has a perforated seal, allowing for easy opening of the plastic bag when the medication is needed.

Life expectancy in the United States, and around the world, has been slowly rising each year. Cleaner water, better sanitation and nutrition, and a greater access to medical services has allowed individuals to live fuller and longer lives. Medical science continues to forge ahead in discovering new treatments and procedures to combat diseases and conditions that have plagued humans for centuries.
Among the continuing innovations in the medical sciences is the increasing amount of pharmaceutical treatments available for a variety of illnesses. Diseases that were once virtual death sentences, such as HIV, can now be managed through a strict regimen of pharmacological treatments. Additionally, more and more people are taking an increasing number of daily vitamins and supplements as prophylaxis against illness.
Unfortunately, keeping track of a daily regimen of pills can be a herculean task, especially when the regimen requires a strict adherence for effective treatment. Some treatments require dozens of pills daily. While many pill sorters have appeared in the market place, most do not allow for the easy arrangement of pills, nor do they allow the user to easily carry pills around on their person, especially when the user might be travelling to a remote location. What is needed is a pill sorting system that allows a user to sort medications and seal them into easily opened bags for transport.


The invention comprises an aqueous solution comprising a water-soluble, polyamidoamine- epichlorohydrin resin, said solution having a reduced halogen content and effective wet strength agent properties, obtained by subjecting an aqueous solution comprising a water-soluble polyamido-amine-epichlorohydrin resin to an organic halogen content reducing after-treatment wherein the total halogen content is below 1% by weight, calculated on solid resin and the halogen content is below 0.1% by weight.

The invention pertains to a process for the preparation of a water-soluble, nitrogen-containing, epihalohydrin-based resin comprising the step of subjecting the resin to an organic halogen reducing after-treatment.
Resins of the above type, mainly polyaminoamide-epihalohydrin resins, are well-known and find wide usage as wet-strength agents for paper. Epihalohydrin is known to impart wet-strength efficacy to polyaminoamides, but also causes the eventual resins to contain large amounts of organic halogen. A significant number of efforts to overcome this problem while retaining the product""s wet-strength imparting effect has been reported.
Thus, a process of the type mentioned in the opening paragraph, which can be based on conventional previous reaction steps, e.g. comprising the reaction of polyaminoamide and epihalohydrin, is known from published European Patent Application No. 0 349 935. Said step consists of contacting the prepared resin with a base to convert it into a product having a pH  greater than 8, after which neutralization can take place. In this manner the organic chlorine content can be reduced to as little as 1% by weight. However, it is disclosed that, irrespective of the extent of the reduction of the organic chlorine content, the total chlorine content will remain unchanged. This is a serious limitation of the effect of the after-treatment, the remaining inorganic chlorine being a potential source of newly formed organic chlorine since it is the aqueous resin solution in which a new equilibrium will be established.
The invention has for one of its objects to obviate this drawback by providing a method for reducing the total chlorine content. Also, the invention meets the objective of further reducing the content of organic halogen without the resin""s favourable properties being adversely affected.
In order to meet these and other objectives, the invention consists in that in a process of the above-described known type the after-treatment comprises contacting the resin with a basic ion-exchanger.
Unexpectedly, the after-treatment according to the present invention results in the resin subjected to it having a surprisingly low total halogen content of 1% by weight or lower, calculated on solid resin. It should be noted that in EP 369 935 the total halogen content remains at a level of 13,52% by weight, calculated on solid resin. So, clearly, the process according to the invention results in an unobvious improvement, further evidenced by the fact that the total halogen content in the novel resins prepared in accordance with the invention is even lower than the organic halogen content of the known resins.
Evidently, the total halogen content of the resins prepared in accordance with the present invention being considerably lower than in known resins, the resulting organic halogen content is lower also, viz. below 0,1% by weight, calculated on solid resin. In this respect it should be noted that the following art-recognized definitions of halogen contents apply to the description of subject invention:
Total halogen content obviously indicates all halogen present and this is the sum of all organic and inorganic halogen present.
Organic halogen content indicates all halogen linked to organic molecules, i.e. total halogen minus inorganic halide ions.
Adsorbable organic halogen, hereinafter referred to as AOX, is a term widely used in the art of wet-strength agents for paper. It indicates all organic halogen that can be determined by means of adsorption onto activated carbon using the method according to DIN 38409, part 14.
By-products content refers to 1,3-dihalo-2-propanol (DXP) and 1-halo-2,3-propane diol (MXP), which are the most important undesired by-products formed when a resin is prepared from a reaction mixture containing epihalohydrin. Since the most common epihalohydrin in the art is epichlorohydrin, by-products content frequently indicates DCP (dichloro propanol) and MCP (mono chloro propane diol).
A different approach towards low halogen contents is followed in EP 335 158, which discloses substitution of epihalohydrin by halogen-free crosslinkers. The crosslinker being allowed to contain a maximum of 15 mole % epihalohydrin, the resin is not an epihalohydrin-based resin in accordance with the present invention. Particularly low halogen values are disclosed if no epihalohydrin is present at all.
Several other processes for the preparation of water-soluble, nitrogen-containing, epihalohydrin-based resins with reduced halogen contents have been reported, but the halogen contents of the resins prepared by the disclosed processes by no means approximate the low level of the novel resins prepared in accordance with the present invention.
EP 282 862, which discloses a process of the type mentioned in the opening paragraph in which the after-treatment consists of reacting the epihalohydrin-based reaction products with a base followed by conversion with halogen-free acids, presents an organic halogen content of 2,73% by weight, calculated on solid resin. EP 332 967, which discloses a process similar to the EP 282 862 process but in which essentially a mixture of polyamines is applied, presents an organic halogen content of 0,74%, calculated on solid resin. Another disclosure, EP 374 938, only demonstrates a reduced by-product content when referring to organic halogen. The products prepared in accordance with the present invention not only display unexpectedly low total and organic halogen contents, but also unexpectedly low AOX and by-products contents.
It is noted that basic ion-exchangers are known to remove inorganic halide ions. It should be stressed that this does not at all suggest their aiding in the removal of organic halogen, let alone the present finding which provides a significant reduction of total halogen, organic halogen, AOX, and by-products contents and thus presents a solution to a serious problem in the art. The nature of the frequently complicated processes disclosed, which typically includes the alteration of several process parameters, does not at all suggest that a relatively simple after-treatment as applied in accordance with the present invention would have such an impact on the total halogen content, let alone the organic halogen, AOX, and by-products contents. The after-treatment, which in itself can be carried out in a simple manner, generally results in novel products having a total halogen content of below 1% by weight, an organic halogen content of below 0,1% by weight, an AOX content of below 0,002% by weight and by-product contents of below 0,025% by weight of DXP and 0,005% by weight of MXP, calculated on solid resin.
In order to perform the process of the present invention it is a requirement to use a basic, preferably strongly basic ion-exchanger. Ion-exchangers are known in the art and can generally be described as solid substances which upon contact with an electrolyte solution are capable of taking up ions (either positive or negative) and exchange these for an equivalent amount of different ions bearing the same sign. Though the invention process is not limited with respect to the specific type of ion-exchanger used, the most important class of materials is formed by ion-exchanger resins, more specifically synthetic resins. Ion-exchangers of this kind generally comprise a high polymer network of hydrocarbon chains that acts as a matrix for charge-carrying groups linked to it. Basic ion-exchangers generally carry cationic groups such as xe2x80x94NH3+, xe2x95x90NH2+, xe2x95x90N+, xe2x80x94S+. Ion-exchanger resins can be regarded as polyelectrolytes that, due to their crosslinked matrix structure, swell in water rather than dissolve. Since ion-exchangers belong to the common knowledge of the skilled artisan, a detailed explanation need not be given here. Reference is made to Ullmann, Encyclopadie der Technischen Chemie, which has a chapter on ion-exchangers (in the 1957 edition this is Volume 8, pages 787 ff.). Good examples of basic ion-exchangers that can be used in the process of the present invention include those listed in the table given by Ullmann (above edition, page 817). Other basic ion-exchangers, e.g. those based on a polystyrene or polyacrylic matrix, are equally suitable, and admixed resins can also be applied.
Preferably, the ion-exchangers used in the process of the present invention contain tertiary amino and/or quaternary ammonium groups. Strongly basic ion-exchangers are greatly preferred over weakly basic ion-exchangers. Good examples of such ion-exchangers include resins carrying quaternary ammonium groups having three lower alkyl substituents or quaternary ammonium groups containing at least one lower alcohol substituent. Mixed resins can also be applied. The highest preference is given to ion-exchanger resins of a type carrying quaternary ammonium substituents selected from the group consisting of trimethyl ammonium, dimethylethanol ammonium, and mixtures thereof. Applying these most preferred strongly basic ion-exchangers results in epihalohydrin-based resins having a total halogen content of below 0,5% by weight and an organic chlorine content of below 0,05%, calculated on solid resin. It has been possible to reduce the AOX content to even below 0,0005% by weight and to reduce the by-products content to below 0,005% by weight of DXP and 0,003% by weight of MXP.
A detailed, unlimitative description of the after-treatment in accordance with the present invention typically is as follows:
the ion-exchanger resin to be used is transferred from the chloride form (as it is frequently available) to the hydroxy form (regeneration) and washed
mixing with regenerant is continued until regeneration is completed
a solution of epihalohydrin-based resin (up to 20% solids content) is passed through the exchanger resin bed, after which the exchanger resin is washed.
A typical dwell time for the epihalohydrin resin to be in contact with the ion-exchanger bed generally is of the order of about 2 hours, but dwell times of less than 1 hour are preferred.
The after-treatment in accordance with the present invention can basically be preceded by any known process for the preparation of epihalohydrin-based resins. Such processes include those disclosed in the above-referenced European Patent Applications, which are all incorporated by reference for all purposes. Further disclosures of processes for the preparation of water-soluble, nitrogen-containing, epihalohydrin-based resins are found in EP 74 558, U.S. Pat. No. 3 311 594, U.S. Pat. No. 4 336 835, U.S. Pat. No. 3 891 589, and U.S. Pat. No. 2 926 154, which are all incorporated by reference for all purposes. The process according to the present invention may also comprise subjecting commercially or otherwise readily available epihalohydrin-based resins to the after-treatment described hereinbefore. A more detailed description of typical examples of epihalohydrin-based resins will follow below, after a discussion of the novel products to which the invention also pertains.
The invention pertains also to novel, water-soluble, nitrogen-containing, epihalohydrin-based resins obtainable by the above described process. The novel resins fulfill the requirement of having reduced AOX and by-products contents and are characterized by having a total halogen content of below 1% by weight, calculated on solid resin. As is also clear from the above, these novel resins constitute a surprising and unexpected finding, since in view of EP 349 935 the artisan would not expect an epihalohydrin-based resin with a total halogen content even lower than the disclosed organic halogen content to be obtainable. In a preferred embodiment, the invention pertains to resins obtainable by a process involving the after-treatment described hereinbefore which display a total halogen content of below 0,5% by weight, calculated on solid resin.
The total halogen content for the invention resins being considerably lower than in known resins, the organic halogen content is lower also. In this respect the invention also pertains to novel resins having the unobviously low content of below 0,1% by weight of organic chlorine, calculated on solid resin. Even further preferred invention resins are obtainable, viz. those displaying an organic halogen content of below 0,05% by weight, calculated on solid resin. As is clear from the earlier-discussed disclosures of epihalohydrin-based resins with reduced halogen contents, the invention resins cannot be derived from the art in view of their low contents of total chlorine, organic chlorine, AOX and by-products. In this respect the invention also pertains to epihalohydrin-based resins displaying an AOX content of below 0,01% by weight and by-product contents of below 0,005% by weight of DXP and 0,003% by weight of MXP, calculated on solid resin. Preferred resins are obtainable in which the AOX content is below 0,0005% by weight, calculated on solid resin.
Subject water-soluble, nitrogen-containing, epihalohydrin-based resins which are characterized by their novel low halogen contents and are obtainable by the novel process described hereinbefore, can basically be of any type known in the art of paper wet-strength agents. In addition to the above-referenced and incorporated disclosures, preferred resins can be as follows.
Subject resins, also referred to as cationic thermosetting resins, generally comprise a nitrogen-containing precursor and a halogen-containing crosslinker. The resins according to the invention preferably are of the type commonly referred to as polyaminoamide-epihalohydrin resins. Epihalohydrins used in preparing such resins include, particularly, epibromohydrin andxe2x80x94preferablyxe2x80x94epichlorohydrin. A typically preferred mole ratio is 1,3-0,7 moles of epihalohydrin per mole of basic nitrogen in the polyaminoamide. The epihalohydrin is generally comprised in the crosslinker. In preferred epihalohydrin-based resins at least a substantial part of the crosslinker is epihalohydrin, while more preferably epihalohydrin is a major part thereof, particularly about 50 to 100 mole %. It is highly preferred that the crosslinker consist of more than 80 mole % epihalohydrin.
The basic ingredient for the preferred resins is the polyaminoamide reaction product of a polycarboxylic, usually dicarboxylic acid and a polyamine. Suitable polycarboxylic acids include aliphatic, saturated or unsaturated, or aromatic dicarboxylic acids. Preferably, the polycarboxylic acids contain less than 10 carbon atoms. For the purpose of the invention, the term xe2x80x9ccarboxylic acidxe2x80x9d is meant to include carboxylic derivatives also, such as anhydrides, esters or half esters.
Suitable polycarboxylic acids and derivatives include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid. Mixtures of these acids can also be applied. The preferred polycarboxylic acid is adipic acid.
Suitable polyamines include polyalkylene polyamines, or mixtures thereof, satisfying the following formula:
in which R1-R4 represent hydrogen or lower alkyl, preferably up to C3 and a-c represent integers from 0-4. Preferred polyalkylene polyamines include diethylene triamine, triethylene tetra amine, tetraethylene penta amine, dipropylene triamine, and mixtures of these amines.
The polyamines of formula I can very well be combined with other polyamines or mixtures of other amines. Preferably, these amines satisfy the following formulae II-VII.
in which R5-R13 represent hydrogen or lower alkyl, preferably up to C3, d-k represent integers from 0 to 4, and l represents an integer from 1 to 5.
The polycarboxylic acid and the polyamine typically are applied in a mole ratio of from 1:0,7 to 1:1,5.
A water-soluble, nitrogen-containing, epihalohydrin-based resin is generally prepared from a polyaminoamide solution. The solution preferably is aqueous and can be formed of pure water or of water in admixture with a water-miscible solvent, such as ethanol or dimethyl formamide. Many different ways of performing the reaction of epihalohydrin with polyaminoamide have been described, among others in the disclosures previously incorporated hereinto. So, reaction temperatures can be either low or high and various temperature profiles can be applied. Also, reactant concentrations may vary within a broad range. Preferably, the reaction is carried out in such a way that the end-product viscosity at 20xc2x0 C. for a 10% solids content solution is in the range of 10-20 mPa.s, more preferably about 15 mPa.s. If 30% solids content solutions are prepared, the viscosity at 20xc2x0 C. preferably is in the range of 150-250 mPa.s, more preferably about 200 mPa.s. The resulting molecular weights may be as low as 2000, but preferably are in the range of from 100 000-1 000 000 or higher.
The resins according to the present invention are preferably obtained by first subjecting the epihalohydrin-based, nitrogen-containing resins to the ion-exchanger treatment described hereinbefore, and then neutralizing with acid to obtain a product having a pH of, preferably, lower than 5. More preferably, the pH is adjusted to a value between about 3 and about 4.5. Resins having such preferred pH values display a better stability upon storage. It is also possible to first neutralize and then conduct the after-treatment according to the present invention. Neutralization may take place in any manner known in the art, applying any feasible inorganic or organic acids. Preferred organic acids include formic acid and citric acid, whereas preferred inorganic acids include sulfuric acid and phosphorous acid. Mixtures of acids can be applied as well.
As indicated above, the resins according to the present invention can also be obtained by subjecting commercially available water-soluble, nitrogen-containing, epihalohydrin-based resins to the ion-exchanger treatment, by virtue of which novel resins are obtained which have a halogen content reduced by 95% or more.
It should be noted that, though the ion-exchanger treatment is referred to as an after-treatment, it can also be applied during preparation of the water-soluble, nitrogen-containing, epihalohydrin-based resin. In this respect a preferred embodiment of the present invention resides in a resin obtained by a two-stage process. Such a process is basically known from previously incorporated U.S. Pat. No. 3,891,589. The ion-exchanger treatment can be applied after either the first or the second stage. A further preferred process can be described as a three-stage reaction in the following manner:
(a) reacting a polyalkylene polyamine of type I described hereinbefore, optionally in admixture with a polyamine of type II-VII described hereinbefore, with a dicarboxylic acid, preferably an aliphatic dicarboxylic acid, to form a polyaminoamide (PAIM);
(b) reacting the PAIM formed under (a) with an epihalohydrin (EHH) at a temperature of below about 40xc2x0 C. to form a PAIM/EHH adduct;
(c) subjecting the adduct formed under (b) to a temperature in the range of from 50 to 70xc2x0 C. to effect ring-closure and to obtain a precursor resin at a low degree of crosslinking;
(d) subjecting the precursor resin formed under (c) to treatment with a basic ion-exchanger to obtain a substantially halogen-free intermediate;
(e) keeping the intermediate obtained under (d) at alkaline pH and subjecting it to a temperature below 40xc2x0 C. in order to form a water-soluble, nitrogen-containing, epihalohydrin-based resin;
(f) adjusting the pH to neutral or slightly acidic.
The temperature requirements given above should not be interpreted in a too strict sense. The quintessence of the three-stage process is that full crosslinking does not occur until after the removal of halogen. By virtue of the alkaline pH after the ion-exchanger treatment the intermediate obtained under (d) will be subject to crosslinking at relatively low temperatures. Of course, one can also lower the pH and consequently carry out crosslinking at a higher temperature. The resins thus prepared display the lowest levels of total halogen, organic halogen, AOX, and by-products. It is not excluded that halogen-containing by-products can be removed entirely, but this cannot be definitely concluded on the basis of the current detection methods.
The novel resins according to the present invention are useful as wet-strength agents for paper. As such, they have the advantage of avoiding the halogen and halogen-containing by-products contamination normally associated with using epihalohydrin-based resins in paper mills, while retaining their good wet-strength imparting properties. Hence the invention also pertains to the use of the resins described hereinbefore as wet-strength agents for paper.

Epihalohydrin-based resins having a reduced halogen content