ORTHOMETALLATED CATALYST COMPONENTS FOR OLEFIN POLYMERIZATION AND COPOLYMERIZATION

Abstract

Aromatic complexes featuring metal-aryl bonds, active in propylene and other alpha olefin polymerizations are described herein. They are prepared by a single step reaction of readily available ligands Ar.sub.x-L-E with MXy, wherein: Ar=Aryl sigma bonded to L, L=Heteroaromatic or heteroaliphatic ring, with one or more heteroatoms, including fused derivatives, E=Heteroatom on L, available for coordination with the metal. M=Transition metal from groups 3-6, 8, and the lanthanide series of the periodic table of elements. X=Halogenide, y=integer. The ligands react with the TiCl.sub.4 present on MgCl.sub.2 supported polypropylene catalysts and impart substantial activity and other enhancements. They may be used as ethylene or propylene polymerization and copolymerization with higher alpha-olefins, activated with aluminum alkyls such as triethylaluminum.

Claims

1. A method to produce an alpha-olefin polymerization catalyst comprising the steps of: reacting: (a) a compound characterized by the formula:
Ar.sub.X-L-E wherein Ar is phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl or their isomers. For example, naphthyl can be 1- or 2-naphthyl, biphenyl can be 1-, 2-, or 3-biphenyl, anthracenyl can be 2-, or 9-anthracenyl, phenanthrenyl can be 1-, 2-, 3-, or 9-phenanthrenyl. Ar is bonded to L; wherein x is an integer from 1 to 15, more preferred 1-5 wherein L is one of the following: i. a heterocyclic ligand, wherein heterocyclic refers to aromatic or aliphatic, 3 to 7, or higher member rings containing one or more heteroatoms, wherein heteroaromatic rings may include pyridine, pyrimidine, pyrazine, pyrrole, furan, imidazole, pyrazole, triazole, thiazole, isothiazole, oxazole, isoxazole, oxadiazole, phospholene, phospholene oxide, phosphorine (analogue of pyridine containing P), and benzo-fused analogues of these rings such as indole, carbazole, benzofuran, benzothiophene, purine, 2H-chromene, xanthene, and the like, and heteroaliphatic rings such as ethylene oxide (oxirene), ethylenimine (aziridine), trimethylene oxide (oxetane), tetrahydrofuran, purrolidine, piperidine, dioxane, morpholine, trimethylene sulfide, 1,3-diacetidine, 1,2-oxathiolane, oxepane, azocane, thiocane, and the like; ii. Unsaturated cyclic ketones which may include cyclopentadienone, cycloheptatrienone, their sulfur and imino analogues; or iii. Functional group moieties: COR, NRR, SR, PRR, OR, NN, NCR, and the like, directly bonded to Ar, as defined above. R, R, R, the same or different, are separately H, alkyl, or aryl. Examples are benzophenone, diphenylamine, diphenylether, triphenylphospine, triphenylphospine oxide, anisole, and the like, wherein E is a heteroatom, included in L, available for coordination with the transition metal; and (b) a metal halogenide, wherein a metal of the metal halogenide is selected from groups 3-6, 8, and the lanthanide series of a periodic table of elements.

2. The method of claim 1, wherein the Ar.sub.x-L-E compound is 2-phenyl indole, 2,3-diphenyl indole, 2-biphenyl indole, 2,5-diphenyl furan, diphenyl isobenzofuran, 2,5-diphenyl oxazole, 2,3-diphenyl indenone, tetraphenyl cyclopentadienone, 5-phenyl-1,3,4-oxathiazole-2-one, plus all the formulas in Table 1.

3. The method of claim 1, wherein the metal halogenide is TiCl4, TiBr4, TiF4, ZrCl4, HfCl4, CrCl3, VCl3, SmCl3, YCl3, TaCl3, NbCl3, TaCl5, NbCl5, RuCl3, IrCl3, PtCl4, RhCl3, PdCl2, FeCl3, FeCl2, NiCl2, NiBr2, CoCl2.

4. The method of claim 1, with the reaction carried out in solution of aromatic, aliphatic or chlorinated organic solvents, n solvents, under a blanket of nitrogen or argon, toluene being the preferred solvent.

5. The method of claim 1, with the reaction carried out at temperatures between 50 C. and 160 C., preferably between 80 C. and 140 C., and more preferably between 100 C. and 120 C.

6. A product resulting from the method of claim 1, from the reaction of 2-phenyl indole with TiCl.sub.4, the composition comprising the following new composition of matter: ##STR00015##

7. A product resulting from the method of claim 1, from the reaction of 2-phenyl indole with ZrCl.sub.4, the composition comprising a new composition of matter with the same structure as in claim 6, but with Zr in place of Ti.

8. A product resulting from the method of claim 1, wherein two or more Ar.sub.x-L-E compounds participate in the reaction, with one or more metal halogenides.

9. The product of claim 6 with aluminum alkyls AlR.sub.3, triethylaluminum AlEt.sub.3 (TEA), tri-isobutyl aluminum Al(i-Bu)3 (TIBA) and the like, comprising the chemical formula: ##STR00016## Wherein the Al moiety in this formula is represented by the formula AlRzCl.sub.3-z, (z is any number between 0 and 3), R is alkyl, comprising 1 to 20 carbon atoms), and varies with the reaction conditions.

10. The product of claim 9 forming a secondary product by the reaction with an electron donor, comprising ester, ether, ketone, amine, phoshine, and the like.

11. The product of claim 9 further reacted with ethylene, comprising the two formulas shown in Scheme B.

12. The product of claim 9 further reacted with an alpha-olefin, propylene or higher, comprising the four formulas shown in Scheme C from a 1,2-insertion, and another four from a 2,1-insertion.

13. The product of claim 9 further reacted with acetylene or other alkyne.

14. The method of claim 1 wherein the ligand Ar.sub.x-L-E is mixed with other internal modifiers of MgCl.sub.2 supported TiCl.sub.4 polypropylene catalysts, one of: butylphthalate esters, succinate esters, 1,3-dialkyl diethers, organic carbonates, sulfonyl compounds, organosilicon compounds, ketone-ether derivatives, aliphatic cyclic esters, 1,8-naphthyl-diaryloates, esters of dialcohols, during corresponding catalyst preparations at molar ratios modifier/Ar.sub.x-L-E from between 95/5 to 75/25, most preferred between 90/10 to 83/17.

15. The product of claim 6, activated with aluminum alkyls under propylene polymerization conditions to form a stereoregular polymer.

16. The aluminum alkyls of claim 15 are triethylaluminum, and tri-isobutyl aluminum, optionally MAO or ammonium perfluoroborates or mixtures thereof.

17. The product of claim 9, in combination with a MgCl.sub.2 supported TiCl.sub.4 catalyst, and optionally delivered mixed with the aluminum alkyl activator, for the production of isotactic polypropylene and other stereoregular polypropylenes.

18. The product of claim 6, applied in polymerization of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and higher alpha-olefins, styrene, cyclic alkenes, dienes, functionalized alpha-olefins, and combinations thereof.

19. The method of claim 14 comprising a gas-phase, bulk, suspension, or solution.

20. The product of claim 6, wherein the product is supported on silica, silica-alumina, their fluorinated analogues, and used in olefin polymerization.

21. The product of claim 6, wherein the method further comprises the step of producing an adhesive through a high temperature solution polyolefin processes.

22. The product of claim 21, wherein the temperature of the process is between ambient and 250 C., preferably between 100 C. and 220 C., and more preferably between 140 C. and 200 C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0026] FIG. 1 of the drawings is a graphical representation of 13C NMR CPMAS (A) and DDMAS (B) Spectra of 2-Phenyl Indole/TiCl4 Complex;

[0027] FIG. 2 of the drawings is a graphical representation of 13C NMR Assignments of 2-Phenyl Indole, the Reaction Product with TiCl4, and the Final Reaction Product with AlEt3;

[0028] FIG. 3 of the drawings is a graphical representation of IR Spectrum of 2-Phenyl Indole/TiCl4 Complex;

[0029] FIG. 3A of the drawings is a graphical representation of IR Spectrum of 2-Phenyl Indole/TiCl4 Complex;

[0030] FIG. 4 of the drawings is a graphical representation of 13C NMR CPMAS Spectra of the Reaction Product of 2-Phenyl Indole/TiCl4 Complex with AlEt.sub.3;

[0031] FIG. 5 of the drawings is a graphical representation of 13 NMR CPMAS Spectra of 2-Phenyl Indole/ZrCl4 Complex. The Peak at 181 ppm corresponds to ZrC Bond;

[0032] FIG. 6 of the drawings is a graphical representation of 13C NMR DDMAS Spectra of 2-Phenyl Indole/ZrCl4 Complex;

DETAILED DESCRIPTION THE DISCLOSURE

[0033] The orthometallated complexes of the present disclosure may be prepared in pure toluene as the solvent, or other suitable aromatic or aliphatic hydrocarbons at elevated temperatures, by the reaction of a transition metal chloride or other halogenide, oxychloride, thionylchloride and the like, complexes of said compounds with tetrahydrofuran (THF) or other ethers, and mixtures thereof, with ligands having the general formula:

Ar.sub.x-L-E

[0034] where:

[0035] Ar=phenyl, biphenyl, naphthyl, phenanthrenyl, anthracenyl, or their isomers. For example, naphthyl can be 1-, or 2-naphthyl, biphenyl can be 1-, 2-, or 3-biphenyl, anthracenyl can be 2-, or 9-anthracenyl, phenanthrenyl can be 1-, 2-, 3-, 4-, or 9-anthracenyl.

[0036] L=Heteromatic three to seven or higher member ring that contains one or more heteroatoms, the same or different. Specific heteroaromatic rings include, but not limited, to pyridine, pyrimidine, pyrazine, pyrrole furan, imidazole, pyrazole, triazole, thiazole, isothiazole, oxazole, isoxazole, oxadiazole, pospholene, phospholene oxide, phosphorine, and their benzo-fused analogues of these rings such as indole, carbazole, benzofuran, benzothiophene, and the like.

[0037] Also, heteroaliphatic, saturated or unsaturated, three to seven or higher member ring that contain one or more heteroatoms, the same or different. Specific heteroaliphatic rings include, but not limited, to ethylene oxide (oxirene), ethylenimine (aziridine), trimethylene oxide (oxetane), tetrahydrofuran, pyrrolidine, piperidine, dioxane, morpholine, trimethylene sulfide, 1,3-diacetidine, 1,2-oxathiolane, oxepane, azocane, thiocane.

[0038] Also, hydrocarbyls containing functional groups such as COR, NRR, SR, PRR, OR, NN, CHN directly bonded to Ar as defined above. Specific examples include, but not limited to benzophenone, diphenylamine, diphenylether, triphenylphosphine, triphenylphosphine oxide, anisole, and the like.

[0039] E=Heteroatom available for coordinarion with the metal, and is part of L. The distinction is made because L may contain more than one heteroatoms, which may not be available for coordination.

[0040] Specific examples of transition metal reagents employed in this disclosure include, but not limited, to TiCl.sub.4, ZrCl.sub.4, HfCl.sub.4, VCl.sub.3, VF.sub.3, VOCl.sub.3, V(THF).sub.3Cl.sub.3, CrCl.sub.3, CrF.sub.3, Cr(THF).sub.3Cl.sub.3, SmCl.sub.3, YCl.sub.3, TaCl.sub.3, TaCl.sub.5, NbCl.sub.3, NbCl.sub.5, FeCl.sub.2, FeCl.sub.3, NiCl.sub.2, NiBr.sub.2, NiBr.sub.2.CH3OCH2CH2OCH3, NiF.sub.2, CoCl.sub.2, CoBr.sub.2, CoF.sub.2, CoI.sub.2, PdCl.sub.2, PdBr.sub.2, PdI.sub.2, Pd(CF.sub.3CO.sub.2).sub.2, PtCl.sub.2, PtCl.sub.4, PtBr.sub.2, PtBr.sub.4, RhCl.sub.3, IrCl.sub.3, RuCl.sub.3, OsCl.sub.3.

[0041] Preferred reagents are TiCl.sub.4, ZrCl.sub.4, HfCl.sub.4, VCl.sub.3, PdCl.sub.2, most preferred are TiC.sub.4 and ZrCl.sub.4. Specific examples of Ar.sub.x-L-E ligands are the following:

##STR00001## ##STR00002##

##STR00003## ##STR00004## ##STR00005## ##STR00006## ##STR00007## ##STR00008## ##STR00009##

[0042] Preferred ligands are 2-phenyl-indole, 2,3-diphenyl-indole, 2,5-diphenyl-oxazole, 2,5-diphenyl-1,3,4-oxadiazole, 2,3-diphenyl-1-indenone and tetraphenylcyclopentadienone. Most preferred are 2-phenyl-indole and 2,5-diphenyl-oxazole.

[0043] In a most preferred embodiment, one mole of TiCl.sub.4 reacts with two moles of 2-phenyl-indole in toluene at 100 C. to 105 C. under a dry nitrogen atmosphere, to yield the orthometalated complex IV, according to the following mechanism:

##STR00010##

[0044] The structure of compound IV, representing a new composition of matter, was elucidated by elemental analysis, solid-state .sup.13C NMR spectra, infrared spectra, and computational analysis. The incorporation of HCl in IV, observed for the first time in a Ti complex, has been reported in several other crystal structures, B. H. Ward et al, Chem. Mater., 1998, 10 (4), pp. 1102-1108. Also in Ph.sub.4As.sup.+Cl.sup.HCl.

[0045] The starting molar ratio of 2:1 of 2-phenyl indole to TiCl.sub.4 is very important, since a different ratio like 1:1 leads to different reaction products. This fact is related to the formation of a 2:1

##STR00011##

initial complex like I, II, unlike the 1:1 complex V shown below:

[0046] During complexation of 2-phenyl indole with TiCl.sub.4, the former isomerizes to the indolenine structure (as in II, with hydrogen migration to the 3 carbon position, and a double bond shift to the 1-2 position), which represents a thermodynamically more stable form for the complex. In the preferred embodiment of 2:1, one mole of 2-phenyl indole is recovered unreacted, along with the final product IV. The trans octahedral bipyramidal configuration of the reaction precursor II is essential for the orthometalation reaction. The bipyramidal confiuration could also be achieved by the presence of one mole 2-phenyl indole, and a mole of another donor compound, such as an amine, a ketone, an ester, etc. Complex IV is also formed in-situ during preparation of magnesium chloride supported Ti chloride catalysts, when mixtures of DNBP and 2-phenyl-indole are introduced as internal modifiers. This part of the disclosure will be discussed in detail.

[0047] In another aspect of this disclosure the Ar.sub.X-L-E ligands may be polymer-bound, typically on a polystyrene backbone. Several of these materials have a variety of applications including use as supported catalyst components in many chemical reactions, including polymerization. A great number of polymer-bound ligands are commercially available from various sources, particularly from Sigma-Aldrich. As part of the present disclosure, we propose the treatment of polymer-bound Ar.sub.X-L-E with one of the transition metal chlorides, preferably TiCl.sub.4 or ZrCl.sub.4, in organic solvents such as toluene, xylenes, chlorobenzene, other chlorinated solvents etc., at elevated temperatures, typically over 100 C., for the formation of an orthometallated, polymer-bound moiety, to serve as catalyst for olefin polymerization.

[0048] Examples of commercially available, polymer-bound ligands are: 9-anthracene carboxamide, 1-hydroxybenzotriazole, 4-(dimethylamino) pyridine, triphenylphosphine, 1-hydroxybenzotriazole, diphenylphosphoryl azide, pyridinium p-toluene sulfonate, bipyridine, piperazine, piperazine, morpholine, 6-thionicotinamide, 4-benzyloxybenzaldehyde, benzophenone oxime, trimethylsilyl sulfonate, 4-benzyloxy-2,6-dimethoxybenzaldehyde, carbonyl imidazole, 2,6-di-tert-butyl pyridine, aniline, benzyltriphenyl phosphonium bromide, piperidine, 4-methoxytrityl chloride, diisopropylamine, thiosulphate, 1-formylpiperazine, isatoic anhydride, hydroxylamine, N-benzyl-N-cyclohexyl carbodiimide, phenol, 2-hydroxyethylmethylphenylsilane, 4-benzyloxybenzylamine, 4-methyl benzydrylamine, 2-chlorobenzydrol, 2-nitrophenol, aminotrityl, 2-iodylbenzamide, 4-hydroxy iodobenzene diacetate, 3-benzyloxybenzaldehyde, methylsulanylmethl, 4-carboxybenzene sulfonamide, dibutylphenylphosphine, p-toluene sulfonic acid, 4-hydroxymethyl benzoic acid, rink amide 4-methylbenzylhydrylamine, 2-chlorotrityl hydrazine, N, N,N-trimethylenetriamine,

[0049] 2-chlorotrityl chloride, 4-benzyloxybenzyl alcohol, triphenylphosphine oxide, 2-chlorotrityl amine, 4-hydroxymethylbenzoic acid-4-methylbenzydrylamine, 4-methylbenzydrylamine hydrochloride, anthranilic acid, 4-nitrophenyl carbonate. For additional functionalized polymers see R. B. Maseto, PhD Thesis, U. South Africa, February 2010, Aromatic Oxazolyl and Carboxyl Functionalized Polymers by Atom Transfer Radical Polymerization, also Azlactone-Functionalized Polymers, Buck et al, Polym. Chem., 2012, 3, 66-80.

[0050] Aromatic polymers may react in solution or in suspension of aromatic solvents such as toluene, xylenes, chlorobenzene or other chlorinated aromatic/aliphatic solvents, with transition metal halides, mainly TiCl4 and/or ZrCl4, at elevated temperatures to form orthometallated moieties. Examples of aromatic polymers include, but not limited to: polyamides, polybenzoxazole, polybenzimidazole, polycarbonate, polyketone, polyetherketone, polyethersulfone, polyphenylenesulfide, polyamide-imide, polyimide, polyarylate, polyetherimide, poly (p-phenylene benzobisthiazole), polysiloxane, polyimide-siloxane. These polymers are well known in commerce under several trade names such as Kevlar,

[0051] Terlon, Kapton, Matrimid, PBT, PBI, PBO, etc. The amount of metal on the polymer after the reaction with metal chloride should be between about 0.1% to about 3%, preferably between 0.5% and 2%, and more preferably about 1%. When the reaction between the polymer and the metal chloride is in solution, control morphology particles may be prepared by using an emulsion technique, for example as outlined in U.S. Pat. No. 5,955,396.

[0052] As in the case of the metallated polymer-bound ligands, the metallated aromatic polymers may be used as catalysts in olefin polymerizations, thus forming aromatic polymer-polyolefin block copolymers. The production of aromatic polymer-polyolefin copolymers, with the methodology of the present disclosure, will have new properties for attractive applications, reducing the cost of several Engineering Thermoplastics.

[0053] Reactions with Aluminum Alkyls and Aprotic Electron Donors

[0054] Complex (IV) reacts with an aluminum alkyl (triethyl aluminum-TEA, tri-isobutyl aluminum-TIBA, etc) in toluene to form complex VI. The Titanium is alkylated and reduced from Ti (IV) to Ti(III), and a new TiAl bimetallic complex is formed by chloride bridging, with the aluminum chloroalkyl of the type AlRzCl.sub.3-z (z=number between 0 and 3), formed during the reaction:

##STR00012##

[0055] Elemental analysis and spectroscopic evidence are in support of structure (VI). An olefin coordinates with complex (VI), initiating the polymerization process. Most importantly, this geometry around the active metal, is perhaps the reason for (VI) being activated with aluminum alkyls, instead of the non-coordinating anions, MAO, perfluoroborates and the like.

[0056] Complex (IV) is the catalytic species responsible for the improved performance of DNBP/2-phenyl-indole magnesium chloride Ti chloride catalysts of this disclosure. Equivalent improved performance was registered in magnesium chloride Ti chloride catalysts with mixed internal modifiers of DNBP and one of the following ligands: 2,3-diphenyl indole, 2,3-diphenyl indenone, tetraphenyl-cyclopentadienone, 2,5-diphenyl furan, diphenyl isobenzofuran, 2,5-Diphenyl oxazole, 2,5-diphenyl-1,3,4-oxadiazole, and 2-(4-biphenyl)-5-phenyl-1,3,4-oxadiazole.

[0057] Several aprotic (not containing active hydrogen) donors may react with (IV) to yield coordination compounds, active in alpha-olefin polymerizations. Aprotic donors are chosen to prevent cleavage of the metal-aryl bond. The list of donors includes, but is not limited, to ethers, esters, ketones, tertiary amines and their oxides, carbonates and thiocarbonates, organic sulfoxides, phoshines and phoshine oxides, silanes and the like. The heteroatom of these donors coordinates with the Ti of (IV), replacing the chlorine bridge originating from the aluminum chloroalkyl.

[0058] Examples of ethers R.sub.1OR.sub.2 are those with R.sub.1 and R.sub.2 aliphatic or aromatic hydrocarbyls, the same or different, containing from 1 to about 20 carbon atoms. Preferred are di-isopropyl, di-n-butyl or di-iso butyl ether and di-isoamyl ether. Cyclic ethers such as tetrahydrofuran may also be used. Thioethers and sulfoxides are also suitable for this application, for example diphenyl sulfide and diphenyl sulfoxide.

[0059] Examples of ketons R.sub.1COR.sub.2 are those with R.sub.1 and R.sub.2 defined as above. Preferred are dipropyl-, dibutyl-, dipentyl-, dihexyl ketones, and benzophenone.

[0060] Alphatic or aromatic mono- or di-esters are particularly useful as electron donors for (II). Examples are ethyl acetate, ethyl benzoate, malonate and succinate diesters, di-n-butyl of di-isobutyl phthalate, di-octyl-phthalate etc. Esters of di-hydroxy compounds described above are particularly useful.

[0061] Another class of attractive donors are aliphatic and/or aromatic carbonates R.sub.1OCOR.sub.2, where R.sub.1 and R.sub.2, the same or different, are as defined above. Examples are dimethyl carbonate and diphenyl carbonates. Thiocarbonates of similar structures are also preferred donors for (II).

[0062] Examples of tertiary amines NR.sub.1R.sub.2R.sub.3 with R.sub.1, R.sub.2, R.sub.3 aliphatic or aromatic hydrocabyls, the same or different, containing from 1 to about 20 carbon atoms. Preferred are tri-n-butyl and tri-iso butyl amine, triphenyl amine, diphenyl benzyl amine. Aromatic amines such as pyridine, and particularly the 2,6-dimethyl- or 2,4,6-trimethyl-pyridine may also be employed. Among the N-oxides of tertiary amines, various isomers of picoline-N-oxide, lutidine-N-oxide, and collidine-N-oxide are preferred.

[0063] Phosphines and phosphine oxides are common donors for this application. Preferred are tributyl phospine, triphenylphospine, and the corresponding oxides. Every known silanes, especially the monoalkoxy alkyl types are preferred. Most preferred is tributyl methoxy silane.

[0064] Mixtures of the aforementioned donors may also be used. Furthermore, it is possible to treat complex (IV) with one or more donors first, followed by the aluminum alkyl treatment, by reversing the above outlined sequence, which is treatment with aluminum alkyl, followed by treatment with a donor. A third alternative is to carry-out the alkyl aluminum and donor treatment simultaneously. The preferred method is treatment with the aluminum alkyl first, followed by the reaction with the donor compound. The reason for this preference is the initial removal of HCl present in the structure of (IV) with triethylaluminum, to yield chloroethylaluminum and ethane, thus avoiding interaction of the donor with HCl. An excess of five or more moles of aluminum alkyl per mole of complex (IV) is required for this treatment.

[0065] There are countless combinations of orthometallated complexes undergoing the trialkyl aluminum with various donors treatment, outlined above. This fact illustrates the versatility and the availability of numerous new catalyst combinations of the present disclosure for the polymerization of alpha-olefins. These catalysts may be supported on silica, silica-alumina, MgCl.sub.2, and other supports, and activated with aluminum alkyls, MAO, or other non-coordinating anions and used in every known polymerization process.

[0066] Insertion of Olefins and other Molecules into Metal-Aryl Bond, Multi-Site Catalysts

[0067] Reference was made in the Background Section to the insertion reaction of olefins into the metal-aryl

[0068] bond and the creation of multi-site catalysts. When ethylene reacts with complex (IV) the two isomers being formed by insertion, are shown in Scheme B. With propylene or higher alpha-olefins, we have the formation of eight isomers, four with an 1,2-insertion as shown in Scheme C, and four with a 2,1-insertion. Each isomer represents a unique site of polymerization, affecting the physical properties of the polymer produced.

##STR00013##

##STR00014##

[0069] Small molecules such as O.sub.2, CO, CO.sub.2, CS.sub.2, COS, and even molecular N.sub.2 are capable of inserting into the Ti-aryl bond (nitrogen fixation), M. E. Vol'pin et al, Chem. Commun. 1038 (1968). Compounds with functional groups such as imines, carbonitriles, aldehydes, ketones, esters, amides, isonitriles, isocyanates, cyanates, thiosyanates, and isothiacyanates. Alkynes insert also into Ti-carbon bond, Tertahedron Letters 33, 1992, p. 6565.

[0070] The insertion reactions provide a platform for the discovery of new and advanced catalysts.

[0071] Reaction of Ligands with Other Transition Metal Reagents

[0072] ZrCl.sub.4 reacts with 2-phenyl indole under the same conditions employed in the analogous reaction with TiCl4. The isolated product had identical structure to (IV), on the basis of analytical and spectroscopic evidence. The ZrCl.sub.4/2-phenyl indole complex undergoes similar transformations with aluminum alkyls.

[0073] The transition metal reagents already mentioned, along with the various examples of ligands in this disclosure, are capable of forming adducts resembling structure (IV), including an orthometallation step. As such, they represent a new class of novel organometallic compounds, highly active in alpha-olefin polymerizations and coplymerizations, when activated with aluminum alkyls such as TEA, TIBA or other chloroalkyls such as diethyl aluminum chloride (DEAC). Furthermore, their applications may extend to other fields, such as health and electronics.

[0074] There are numerous advantages of the complexes of this disclosure, over metallocene catalysts and other coordination compounds in alpha-olefin polymerizations:

[0075] a) The ease of their preparation. The synthesis of complexes of the present disclosure is carried out as a one pot, single-step procedure, using readily available starting materials. It is therefore fast and economical, which makes these catalysts attractive for commercialization.

[0076] b) The preferred activators of these catalysts are aluminum alkyl activators (TEA, TIBA, etc). Non-coordinating anions, MAO, perfluoroborates and the like may also be used.

[0077] c) The complexes are stable at elevated temperatures (110 C. or above), since they are synthesized at those temperatures.

[0078] d) They are versatile in their applications as catalysts in alpha-olefin polymerizations. They act as modifiers of magnesium chloride supported titanium chloride catalysts. They are suitable for stereospecific polymerization and copolymerization of propylene. Supported on silica or other suitable supports, they can be used for the production of polyethylene and its copolymers. They are expected to incorporate higher levels of 1-butene, 1-hexene, 1-octene because they have an open structure. Furthermore, they can be used advantageously in continuous high temperature solution polymerization processes for the production of specialty polymers, adhesives, etc.

[0079] e) The insertion of an olefin into the metal-aryl bond gives rise to the formation of several stereoisomers, resulting in the multi-site behavior of the complexes. This behavior has a profound impact on polymer product properties, especially on MW and MW distribution. From propylene polymerization tests with magnesium chloride supported titanium chloride catalysts incorporating the complexes, we may conclude that the effect is not limited to MW. Activity is markedly increased, the stereoregularirty is higher, other physical properties such as flex modulus, impact properties etc show improvements. The insertion of small molecules and compounds with certain functional groups into the metal-aryl bond, as illustrated earlier, offers additional flexibility for improvements into the catalytic system.

[0080] f) Mixtures of complexes from the present disclosure with metallocenes of various ligand structures or same/different metal centers, as well as other coordination or organometallic compounds may be employed as catalysts, for producing polymers with targeted properties such as ultra high MW, or to achieve additional product and process improvements. These mixtures may be supported on silica, silica-alumina or other supports well known to those skilled in the art. The mixtures may also be used in high temperature solution processes.

[0081] g) Mixtures of orthometallated catalysts with two or more different ligands of this disclosure, or two or more transition metal types may be applied in alpha-olefin polymerization.

[0082] h) Spray-drying, U.S. Pat. No. 5,672,669, or emulsion techniques, U.S. Pat. No. 8,420,562, may be applied to prepare controlled morphology catalysts with the orthometallated complexes of this disclosure.

[0083] o) The orthometallated complexes of present disclosure may be used in every known industrial polymerization process, gas-phase, bulk, slurry, and/or solution. If so desired, a solution of the complexes in a hydrocarbon solvent may be sprayed through a nozel in the polymerization reactor. Alternatively, the solution may be combined with the aluminum alkyl (TEA, TIBA, etc.) stream in the process.

[0084] p) In certain industrial processes such as the stereospecific polymerization of propylene with magnesium chloride supported titanium chloride catalysts, several dimethoxydialkyl silanes are used as external modifiers, to control the stereoregularity of the polymer. The presence of the orthometallated complexes under polymerization conditions may reduce the need for silanes up to 70%, and in certain cases up to 100%. By reducing the level of silanes, an additional polymerization activity in the order of about 15-20% is observed.

EXAMPLES

Example 1

[0085] Preparation and Structural Characterization of the TiCl.sub.4/2-Phenyl Indole Complex (IV)

[0086] Under a dry N.sub.2 atmosphere inside a drybox, with magnetic agitation, a solution of TiCl.sub.4 in toluene was added to a solution of 2-phenyl indole in toluene, at a molar ratio of , at ambient temperature. The temperature was raised to about 105 C. and an oily dark orange product was formed. Heating was turned off, the supernatant decanted, and the remaining was washed four times with toluene. During

[0087] this process the product crystallized. It was further washed five times with hexane, and dried in vacuo. Analytical and spectroscopic evidence indicates that the product is about 97% pure, the remaining being residual hexane.

[0088] The characterization of the structure of (IV) was based on elemental analysis, solid-state .sup.13C NMR, on IR spectra, and on computational chemistry calculations with structural modeling.

[0089] Cross-polarization with magic angle spinning (CPMAS) solid state .sup.13C NMR technique was used. The samples were packed into MAS rotors in dry box, and dry N.sub.2 was used for sample spinning to prevent sample exposure to moisture. Typical CPMAS experimental conditions used were: external magnet=2.35 tesla; CP contact time=2 milliseconds; proton spin-lock radio-frequency field=40 Khz; recycle delay=3 seconds. Dipolar dephasing (DDMAS) technique, with 40 microseconds dephasing time was used to obtain quarternary (and methyl) carbons only spectra, to aid in spectral assignment.

[0090] Both types of .sup.13C NMR spectra for (IV) are shown in FIG. 1. The .sup.13C NMR assignments for each carbon of pure phenyl-indole are presented in FIG. 2. The spectra in FIG. 1 have a small peak at 183 ppm that cannot be assigned to any carbon in pure 2-phenyl indole. The DDMAS spectrum further indicates that this peak is due to a quaternary carbon. There are four more quaternary carbons in (I) which roughly correspond to four quaternary aromatic carbon peaks seen in the spectrum (FIG. 1), though their exact assignment can not be ascertained. Furthermore, an aliphatic carbon peak at ca. 42 ppm due to a nonquaternary carbon, can be assigned to the lone CH2 carbon.

[0091] The 183 ppm peak is assigned to the quaternary carbon directly bonded to Ti through orthometalation, and formation of a five-member metalocycloimine ring.

[0092] The IR spectrum of (IV) is presented in FIG. 3 and FIG. 3A. Four very strong absortions at 418, 410, 398, 375 cm-1 are assigned to v TiCl. By comparison, TiCl.sub.4.DNBP which has an octahedral configuration around Ti, showed maxima at 406, 400, 383, 374 cm-1, Gregory G. Arzoumanidis et al Catalytic Olefin Polymerization, Proceedings of Interanional Symposium, Tokyo, Oct. 23-25, 1989 (Kodanska, Ltd.). A strong band of 2-phenyl-indole at 685 cm-1 characteristic of five consecutive H atoms in a phenyl group, is not present in (IV). Instead, a new band appears at 722 cm-1 assigned to four consecutive H atoms in an aromatic ring, a supporting evidence for the orthometalation of the phenyl group.

[0093] The HCl produced by the orthometalation of the phenyl group is being retained in the structure (IV). There is creation of an Cl . . . HCl species, which has been demonstrated in several other crystal structures, Brian H. Ward et al, Chem. Mater., 1998, 10 (4), pp. 1102-1108, or Ph.sub.4AsCl.HCl, which is an item of commerce.

[0094] The oxidation state of Ti in (IV) was confirmed to be +4 using X-ray photoelectron spectroscopy (XPS). The binding energy (BE) of Ti 2p3/2 photoelectrons in the complex was found to be 458 eV from the XPS data. This value of BE compared to literature data of other Ti compounds suggests +4 oxidation state for Ti.

Example 2

[0095] Reaction of Complex (IV) with Triethylaluminum, Formation of Complex (VI)

[0096] Complex (IV) was suspended in toluene and reacted with excess triethyl aluminum in the dry box at ambient temperature. The product of the reaction was washed several times with toluene, and then with hexane, dried under vacuo.

[0097] During the treatment of (IV) with the aluminum alkyl, the HCl is neutralized through the formation an aluminum chloroalkyl and ethane:

AlEt.sub.3+nHCl=AlEt.sub.3nCl.sub.n+nEtH

[0098] The alkyl aluminum reduces the Ti(IV) to Ti(III) and abstracts an additional HCl from the organometallic moiety as well, by rearranging the double bond in the indole structure back in its original 2,3-position, and formation of a NTi sigma bond. This is illustrated in the .sup.13C CPMAS spectra FIG. 4. There is a new shoulder peak at 108 ppm, which we assign to the new quaternary carbon in the 3 position. The CH.sub.2 carbon previously representing the 3 position in (IV) is not there any more. The peak assigned to phenyl carbon bonded to Ti is shifted further downfield to 196 ppm. The spectrum shows a large peak at ca. 15 ppm from ethyl carbons, indicating alkylation on the Ti, and possible aluminum alkyl incorporated in the structure. The analytical results are consistent with a coordinated chloroalkyl aluminum with the formula AlEt.sub.0.3Cl.sub.2.7 i.e., roughly a mixture of 90% AlCl3 and 10% AlEtCl.sub.2. The ratio of the AlCl.sub.3 and AlEtCl.sub.2 may vary, depending on reaction conditions, reactant ratios, etc. Accordingly, the bimetallic is essentially an AlCl.sub.3 adduct of an alkylated Ti(III)-orthometalated phenyl indole.

Example 3

[0099] Reaction of Complex (VI) with Donor Molecules

[0100] DNBP reacts with (VI) in toluene or other aromatic or aliphatic solvent, under mild conditions at a molar ratio of 2:1, to yield a product wherein the diester replaces AlCl.sub.3 in the complex through coordination of the two carbonyl groups with Ti.

[0101] Numerous other donor molecules recorded in this disclosure are capable of yielding similar adducts, following the same procedure.

Example 4

[0102] Reaction of 2-Phenyl Indole with ZrCl.sub.4

[0103] The procedure outlined in Example 1 was repeated, except ZrCl.sub.4 was used instead of TiCl.sub.4. The isolated product had some residual hexane as impurity, despite being treated in vacuo. The DDMAS and CPMAS solid state 13C NMR spectra of the isolated product (FIG. 5 and FIG. 6) closely resemble those of the TiCl.sub.4 complex (IV). The Zr-aryl bond in .sup.13C NMR is at 181 ppm. This implies that the ZrCl.sub.4 complex is structurally similar to (IV). Analytical data support this interpretation.

Examples 5 through 8

[0104] MgCl.sub.2 Supported Catalyst Preparations with Mixed Donors

[0105] Magnesium chloride supported titanium chloride catalysts were prepared following the procedure by Arzoumanidis et al in U.S. Pat. No. 5,124,297, Example 1. In these preparations mixtures of DNBP/2-phenyl indole at molar ratios of 50/50, 75/25, 85/15 and 80/90 was used.

[0106] The catalyst were tested in a slurry propylene polymerization test, in batch gas phase and in a continuous laboratory gas phase unit.

[0107] The batch hexane slurry polymerization evaluated the performance of propylene polymerization catalyst relative to a control catalyst. The polymerization takes place in a two liter reactor using 1 liter of hexane, 10 mg of catalyst, triethylaluminum, diisobutyldimethoxysilane, and enough H.sub.2 to achieve a melt flow rate of ca. 5 g/10 min. The hexane, catalyst system, H.sub.2, and propylene were added to a cool reactor, and the reactor heated to 160 F. over a 10 min period. The reactor pressure was maintained at 150 psig by feeding propylene on demand. The polymerization was run for 1 hour starting from the time the temperature reached 150 F. At the end of the polymerization, the pressure was vented, the polymer slurry filtered, the polymer dried in a vacuum oven and weighed, and a 100 ml aliquot of the hexane filtrate evaporated to determine percentage soluble portion.

[0108] The batch gas phase polymerization test is described in U.S. Pat. No. 5,124,297.

[0109] The 50/50 and 75/25 catalysts showed activity lower than the control, which is a catalyst prepared with only DNBP as the internal modifier. Also, the powder bulk density of the 50/50 and 75/25 was substantially lower than the control.

[0110] The 85/15 and 90/10 catalysts gave a 40-65% activity improvement over the control, lower extractables and overall better powder bulk density, by about 10%.

Examples 9-15

[0111] MgCl.sub.2 Supported Catalyst Preparations with DNBP Mixed with Various Donors at 85/15 Molar Ratio

[0112] The procedure of the previous Example was followed to prepare MgCl.sub.2 supported catalysts using mixtures of DNBP with seven different donors, at the optimum molar ratio of 85/15 respectively. All the catalysts prepared showed improved performance over the control, as indicated on Table 1.

TABLE-US-00001 TABLE 1 Percent Polymerization Yield Advantage with Several Ligands/Intemal Modifiers mixed with DNBP (DNBP/Donor = 85/15 molar) of MgCl.sub.2 Supported Catalysts Polymerization Test Batch Gas Continuous Gas No Donor Slurry Phase Phase 1 2-Phenyl 36% 48% 65% Indole 2 2,5-Diphenyl 21 35 Furan 3 Diphenyl 27 Isobenzofuran 4 2,5-Diphenyl 46 Oxazole 5 2,3-Diphenyl 40 65 Indole 6 2,3-Diphenyl 54 Indenone 7 Tetraphenyl 61 Cyclopentadienone

[0113] The batch gas phase procedure has been described in the aforementioned patent, Example 1. The continuous gas phase system is similar to the batch, but it is automated for continuous operation.

[0114] It is further understood that various other modifications to these examples may be made to those skilled in the art, within the spirit and scope of this disclosure.

Comparable Example 1

[0115] MgCl.sub.2 Supported Catalyst Preparation with 2-Phenyl Indole as the Internal Modifier

[0116] A MgCl.sub.2 supported catalyst was prepared following the procedure of the earlier Examples, using 2-phenyl indole as the only internal modifier. The activity of the catalyst in batch gas phase polymerization was only 30% of the activity of the control.