MXPA98010497A - Catalyst for the polymerization of alpha-olefins containing aminosilan substitute compounds - Google Patents

Abstract

An aminosilane of the formula, wherein R1 is linear or branched C1-22 alkyl or C3-22 cycloalkyl which may be substituted with at least one halogen atom, R2 is a bis (C1-22 linear or branched alkyl or cycloalkyl) amino) of C3-22, a substituted piperidinyl, a substituted pyrrolidinyl, decahydroquinolinyl, 1,2,3,4-tetrahydroquinolinyl or 1,2,3,4-tetrahydroisoquinolinyl, with the substituent selected from the group consisting of C1-8, phenyl and trimethylsilyl substituted with linear or branched C 1-8 alkyl, with the proviso that when the substituent is C 1-8 alkyl, it must make at least two said substituent groups present and R 1 must contain halogen; is linear or branched C1-8 alkyl or C3-8 cycloalkyl. The aminosilane can be reacted with an aluminum-alkyl compound and a solid component comprising a titanium compound having at least one titanium-halogen bond and an electron donor, both supported on an activated anhydrous magnesium dihalide, to form a catalyst for olefin polymerization

Description

CATALYST FOR THE POLYMERIZATION OF ALPHA-OLEFINS CONTAINING AMINOSILAN COMPOSITES SUBSTITUTED This invention relates to Ziegler-Natta catalyst systems that utilize an amino-substituted silane electron donor as a cocatalyst component. The olefin polymers produced with these catalyst systems exhibit a desirable combination of high isotacticity and high polydispersity index. The isotacticity of a polymer is important in determining its suitability for a given application. Isotacticity is often measured by determining the percent by weight of polymer soluble in xylene at room temperature (XSRT) and subtracting this one hundred percent. A high isotacticity greater than 90 is preferred, and greater than 95 is more preferable. The polydispersity index (P.I.) is a measurement of the molecular weight distribution of a polymer. A broad-scale distribution of molecular weight (high P.O.> > 4.0) provides improved melt strength, which is advantageous in thermoforming, film and fiber forming operations. A P.I. High of 4.0 is indicative of a broad molecular weight distribution. Preferably P.I. is > 4.5, more preferably, 5.0 or greater. The organosilane compounds have been used in catalyst systems (1) as an electron donor in the solid catalyst component which comprises a halogen-containing Ti compound supported on an anhydrous activated Mg dihalide compound and (2) as a hydrogen donor. electrons with the cocatalyst component comprising an organometallic compound. Typically they are organosilane compounds having Si-OR, Si-COR or Si-NR2 bonds, wherein R is alkyl, alkenyl, aryl, arylalkyl or cycloalkyl having 1 to 20 carbon atoms and Si as the central atom. These compounds are described in the patents of E.U.A. Nos. 4,180,636; 4,242,479; 4,347,160; 4,382,019; 4,435,550; 4,442,276; 4,465,782; 4,473,660; 4,530,912 and 4,560,671, where they are used as electron donors in the solid catalyst component; and in the Patents of E.U.A. Nos. 4,472,524, 4,522,930, 4560,671, 4,581,342, 4,657,882 and in European Patent Applications 45976 and 45977, where electrons are used as cocatalyst. The Patent of E.U.A. No. 5,102,892 discloses trifluoropropyl substituted silanes which may also contain a piperidinyl or pyrrolidinyl ring, such as • 3,3, 3-trifluoropropyl-1-pyrrolidyl-dimethoxylamino and 3,3,3-trifluoropropyl-1-methyl-piperidyl-dimethoxysilane. Even more recently, European Patent Publication No. 658,577 teaches that fiber prepared from propylene homopolymers polymerized using trifluoropropyl (alkyl) dimethoxysilane has a lower binding temperature and wider window of binding temperature than the homopolymer fibers of polymerized propylene. using catalysts having conventional electron donors such as phenyl triethoxysilane, dicyclopentyldimethoxysilane and di phenyl-dimethoxysilane. An object of this invention is to provide novel amino silanes useful as electron donors in olefin polymerization catalyst systems. Another object of the invention is to provide an improved catalyst system that produces olefin polymers that they have. a desirable combination of high isotacticity and high polydispersity index. In one aspect, the present invention relates to aminosilane compounds that are formed with the following formula: I R2 wherein Ri is a linear or branched C3-Z2 alkyl or C3.22 cycloalkyl, which may be substituted with at least one halogen atom; R2 is a Cx-22 alkyl or cycloalkylamino of C3-22 bislineal or branched, a substituted piperidinyl, a substituted pyrrolidinyl, decahydroquinolinyl, 1, 2, 3, 4-tetrahydroquinolinyl or 1, 2, 3, -tetrahydroisoqui-nolinyl, with the substituent selected from the group consisting of alkyl of linear or branched C? _8, phenyl, linear or branched C? -B alkyl substituted with phenyl and trimethylsilyl, with the proviso that when substituted C? -B alkyl, there must be at least two of these substituent groups present and R_ must contain halogen; and R3 is a linear or branched C? -S alkyl or C3-8 cycloalkyl. In a second aspect, the present invention relates to a catalyst for the polymerization of olefins, which comprises the reaction product of: (A) an alkyl aluminum compound; (B) aminosilane compounds described above, and (C) a solid component comprising a titanium compound having at least one titanium-halogen bond and an electron donor, both supported on an activated anhydrous magnesium dihalide compound. As summarized above, the aminosilane compounds of the present invention conform to the following formula: OR3 1 I R2 wherein Ri is a linear or branched d-22 alkyl or C3-22 cycloalkyl, which may be substituted with at least one halogen atom; R 2 is bis (C?-22 alkyl or C 3-22 cycloalkyl) linear or branched amino, a substituted pipperidinyl, a substituted pyrrolidinyl, decahydroquinolinyl, 1,2,3-tetrahydroquinolinyl or 1,2,3,4-tetrahydroisoquinolinyl , with the substituent selected from the group consisting of linear or branched C? -S alkylphenyl, phenyl and trimethylsilyl substituted with linear or branched C1-8 alkyl, with the proviso that when the substituent is C? alkyl? T, there must be at least two of these substituent groups present and Rx must contain halogen; and R3 is linear or branched C? -T alkyl or C3-8 cycloalkyl. Preferably,. Ri is 3, 3, 3-trifluoropropyl, and R3 is methyl or ethyl. Illustrative compounds that fall within these preferred definitions include 3,3,3-trifluoropropyl-1- (2-trimethylsilylpiperidinyl) dimethoxysilane; 3, 3, 3-t i fluoropropy1 (2-trimethylsilylpyrrolidinyl) -dimethoxysilane; 3,3, 3-trifluoropropy1 (2- (3-methyl phenyl) piperidinyl) dimethoxysilane; 3,3, 3-trifluoropropyl-2- (3-methyl-phenyl) -pyrrolidinyl) -dimethoxy-ylan; 3,3, 3-trifluoropropy1 (1,2,3, -tetrahydroquinolinyl) -dimethoxysilane; 3, 3, 3-t i fluoropropy1 (1,2,3, -tetrahydroisoquinolinyl) -dimethoxysilane; 3,3, 3-trifluoropropy1 (decahydroquinylinyl) dimethoxysilane; 3,3, 3-trifluoropropy1 (bis (2-ethylhexy1) amino) dimethoxysilane; and 3,3, 3-trifluoropropyl-1 (cis-2,6-dimethylpiperidinyl) dimethoxysilane. The aminosilanes can be prepared by a multi-step synthesis route. The first step is a reaction between the anion of a C?-22 alkane or alkane substituted with halide and a commercially available silane such as tetraalkylorthosilicate (SiOR 4) or tetrachlorosilane. When tetrachlorosilane is used, an (alkyl) trichlorosilane or (substituted alkyl halide (trichlorosilane) results in the (alkyl) trialkoxysilane- or (alkyl substituted with halide) trialkoxysilane by treatment with the appropriate alkoxide (e.g. methoxide or ethoxide) When a tetraalkylorthosilicate is used, the (alkyl) trialkoxysilane or (alkyl substituted with halide) trialkoxysilane is prepared directly The final step is a substitution reaction between the (alkyl) trialkoxysilane or (alkyl substituted with halide) trialkoxysilane and a substituted or cyclic secondary amine.-The amine-anion is generated by treatment with either n-butyl lithium or isopropylmagnesium chloride.The anion is then left to react with the (alkyl) trialkoxysilane or (alkyl substituted with halide) trialkoxysilane for producing aminosilane, it is necessary to use a protective group to prepare certain amines, an appropriate protective group is tert-butylcarbamate ("BOC") which was used to prepare 2-trimethylsilylpiperidine, 2-trimethylsilylpyrolidine, 2- (3-methylphenyl) piperidine and a 2- (3-methylphenyl) pyrrolidine. The BOC group was ligated generating the anion of either piperidine or pyrrolidine using sodium hydride in tetrahydrofuran. This solution was cooled to 5SC and a slight excess of di-tert-butylcarbonate was added. After two hours, the solution was poured into saturated sodium bicarbonate and the layers were separated. The organic layer was dried over magnesium sulfate and the solvent was removed by rotary evaporation. The distillation under reduced pressure provided either piperidinyl-N-tert-butylcarbamate (pe 95SC, 3 mm Hg, 89% yield) or pyrrodinyl-N-tert-butylcarbamate (eg 69BC, 1 mm Hg, 95% yield). The aminosilanes of the present invention can be reacted with an aluminum alkyl compound (A) and a solid component (C) comprising a titanium compound having at least one titanium-halogen bond and an electron donor, both supported by an activated anhydrous magnesium dihalide, to form appropriate catalysts for olefin polymerization. The Al-alkyl compounds which form component (A), which do not contain halogen, include: Al-trialkyl, such as Al-triethyl, Al-triisopropyl, Al-triisobutyl, Al-dialkyl hydrides, such as Al hydride -diethyl, and compounds that contain two or more Al atoms linked together through heteroatoms of oxygen, nitrogen or sulfur, such as: (C2H5) 2A1- -A1 (C2H5) 2; (C2H5) 2A1- -N- -A1 (C2H5); Y (C2HS) 2A1- -0 A1 (C2H5) 2 Preferably, the Al-alkyl compound is Al-triethyl. In the solid component (C), suitable examples of the titanium compound having at least one Ti-halogen bond are Ti-tetrahalides, in particular, TiCl 4. However, alkoxy halides can also be used. The electron donor compounds used in component (C) include alkyl, aryl, and cycloalkyl esters of aromatic acids, especially benzoic acid or phthalic acid, and their alkylphenyl, n-butyl benzoate, p-toluate methyl, diiso ^ ropil phthalate di- -butiiftalate diisob- tilftalato and dioctyl-f alato. In addition to the above esters, alkyl or alkaryl ethers, ketones, mono- or polyamines, aldehyde compounds and phosphorus, such as fnof i pao xr f nofnrar? I lao f-nml-ií pn r-iuorlp * "1 ni * The electron donors are the most preferred.The active anhydrous magnesium dihalides that form the support of component (C) are the dihalides of Mg that show in the dust spectrum. X-ray of the component (C) a broadening of at least 30% of the most intense diffraction line appearing in the powder spectrum of the corresponding dihalide having a surface area of 1 m2 / g or are the dihalides of Mg showing a X-ray powder spectrum in which the most intense diffraction line is replaced by a halo with a peak of intensity displaced with respect to the interplanar distance of the most intense line and / or Mg dihalides having a larger surface area of 3 ra2 / g. The surface area of the Mg dihalides is made in component (C) after treatment with boiling TiCl 4 for 2 hours. The found value is considered as the surface area of the Mg dihalide. The Mg dihalide can be pre-activated, it can be activated in situ during titanation, it can be formed on site from an Mg compound, which is capable of forming Mg-dihalide when treated with an appropriate halogen-containing transition metal compound. , and then activated, or it can be formed from a C1-3 alkanol adduct of Mg dihalide wherein the molar ratio of MgCl2 to alcohol is 1: 1 to 1: 3, such as MgCl2.3ROH. The highly active forms of Mg dihalides are those that show an X-ray powder spectrum in which the most intense diffraction line appearing in the spectrum of the corresponding halide having 1 m2 / g of surface area is decreased in relative intensity and widens to form a halo or are those in which the most intense line is replaced by a halo that has a crest of intensity displaced with respect to the interplanar distance of the most intense line. Generally, the surface area of the above forms is greater than 30-40 m2 / g and is comprised, in particular, between 100-300 m2 / g. The active forms are also those derived from the above forms by thermal treatment of the component (C) in inert hydrocarbon solvents and showing in the X-ray spectrum acute diffraction lines instead of haloes, the acute, more intense line of these In any case, the shapes show a broadening of at least 30% with respect to the corresponding line of Mg dihalides having 1 m2 / g of surface area. The preferred Mg dihalides are MgCl2 and MgBr2 and the most preferred is MgCl2. The water content of the halides is generally less than 1% by weight. By Ti halides or alkoxy Ti halides and electron donors supported on active Mg dihalide is meant the above compounds which can be chemically or physically fixed on the support and non-extractable of the component (C) by treatment of the with 1, 2-dichloroethane in boiling for 2 hours. Component (C) can be made by various methods. One method is to co-grind the Mg dihalide and the electron donor compound until the product, after extraction with Al-triethyl under conventional conditions, shows a surface area greater than 20 m2 / g, as set forth above for the Mg dihalide spectrum, and then reacting the milled product with the Ti compound. . Other methods for preparing component (C) of solid catalyst are described in U.S. Patents. Nos. 4,220,554; 4,294,721; 4,315,835 and 4,439,540, the methods of which are incorporated herein by reference. In all of the above methods, component (C) contains an Mg dihalide present in the active form as set forth above. Other known methods that lead to the formation of Mg dihalide in active form or to components containing dihalide of mg containing Ti, in which the dihalide is present in active form, are based on the following reactions: (i) reaction of a Grignard reagent or an MgR2 compound (R being a hydrocarbyl radical) or complexes of MgR2 compounds with Al trialkyl, with halogenating agents such as AlX3 or AlR "Xn (X is halogen, R is a hydrocarbyl, m + n = 3), SiCl 4, or HSiCl 3; (ii) reaction of the Grignard compound with a silanol or polysiloxane, H20 or with an alcohol and further reaction with a halogenating agent or with TiCl; (iii) reaction of Mg with an alcohol and a halogen halide acid, or of Mg with a hydrocarbyl halide and an alcohol; (iv) reaction of MgO with Cl 2 or AlCl 3; (v) MgX2 reaction. nH20 (X = halogen and n is 1-3) with a halogenation agent or TiCl4; or (vi) reaction of Mg mono or dialkoxides or Mg carboxylates with a halogenating agent. In component (C), the molar ratio between the Mg dihalides and the halogenated Ti compound supported thereon is between 1 and 500 and the molar ratio between the halogenated Ti compound and the electron donor supported on the dihalide of Mg is between 0.1 and 50. The catalyst, ie, the components (A), (B) and (C) can be added to the polymerization reactor by separate means substantially simultaneously, regardless of whether the rnonomer is already in the reactor , or sequentially if the monomer is added to the polymerization reactor later. It is preferred to pre-mix the components (A) and (B), then to contact the premix with the component (C) before the polymerization for from 3 minutes to about 10 minutes at room temperature. The olefin monomer can be added before of, with or after the addition of the catalyst to the polymerization reactor. It is preferred to add it after the addition of the catalyst. The hydrogen can be added as necessary as a chain transfer agent for reduction in the molecular weight of the polymer. It is possible to achieve a melt flow rate of more than 1500 g / 10 minutes using an appropriate amount of hydrogen and the appropriate selection of the aminosilane compound. See Example IX below. Polymerization reactions can be done in suspension processes, liquid or gas phase, or in a combination of liquid and gas phase processes using separate reactors, all of which can be done either batchwise or continuously, polymerization is generally carried out at a temperature of 40-90sC and at atmospheric pressure or a higher pressure. The catalysts can be previously contacted with small amounts of olefin monomer (prepolymerization), keeping the catalyst in suspension in a hydrocarbon solvent and polymerizing at a temperature of 60 ° C or lower for a sufficient time to produce an amount of polymer of 0.5 to 3 times the weight of the catalyst. This prepolymerization can also be effected in liquid or gaseous monomer to produce, in this case, an amount of polymer up to 1000 times the weight of catalyst. The appropriate alpha-olefins that can be polymerized by this invention include olefins of the formula CH 2 = CHR, wherein R is H or branched or straight alkyl of C? _10, such as ethylene, propylene, butene-1, pentene-1,4-methylpentene-1 and octene-1. The following examples are shown to illustrate the invention and are not intended to define the scope thereof, unless otherwise indicated, all parts and percentages in this application are by weight.

EXAMPLES Preparation of Electron Donor Compounds. General Procedures The purity of all the reagents was confirmed either by chromatographic or spectrophotometric analysis. When appropriate, the reagents were purified before use. All non-aqueous reactions were conducted under an atmosphere of dry nitrogen or argon using glassware that was dried under vacuum while heating. The solutions sensitive to air and moisture were transferred through syringe or stainless steel cannula. The boiling points and melting points were uncorrected. The NMR spectra were recorded on a Varian Unity 300 spectrometer operating at 300 Mhz and internally referred to either tetramethylsilane or residual proton impurities. Data for 1H are reported as follows: chemical shift (, ppm), multiplicity (single-s, d-doublet, t-triplet, q-quartet, qn-quintet, m-multiplet), intetration. Data for 13C NMR are reported in terms of chemical shift (, ppm). The infrared spectra were reported on a BiorRad FT430 series mid-IR spectrometer using Kbr plates and reported in terms of absorption frequency (v, cm1). GC analyzes were conducted using a Hewlett Packard Model 6890 Chromotometer using Flame Ionization Detection ("FID") coupled to an HP6890 Model Meter In a typical analysis of 1 0 uL was injected into a 250SC injector (50 1 divided ratio , head pressure of column 0 703 kg / cm2 divided flow of 106 mL / mm, total flow of 111 mL / mm) Helium as used as a carrier gas through an Alltech Heliflex AT-1 column (30 mx 0 32 mm x 0 3 m) The initial temperature was maintained at 50 ° C for two minutes then increased to 10 ° C / mm until a final temperature of 300 ° C The FID detector was maintained at 300 ° C (40 mL / m H2 400 mL / rnin of air constant formation mode using 30 mL / mm of He) Two GC / MS systems were used One system was a Hewlett Packard model 5890 GC coupled to a Hewlett Packard model 5970 mass selective ("MSD") In a typical analysis, 2 0 uL of sample were injected into an injection hole without di vision at 290SC Helium was used as the carrier gas through an HP-1 (Hewlett Packard, 25 -mx 0 3 mm x 0 2 um) The initial temperature was maintained at 75 ° C for four minutes The column was heated to 102 ° C / mm The acquisition of MSD was 10-800 AMU The spectra were reported as m / z (relative abundance) The second GC / MS system was a Hewlett Packard model 6890 GC coupled to a selective mass detector Hewlett Packard model 5973 In an analysis Typically, 1.0 uL of sample was injected into a split / no division injection hole at 290SC. Helium was used as the carrier gas through an HP-5 (Hewlett Packard, 30m x 0.25mm x 0.25um). The initial temperature was maintained at 50 ° C for four minutes. The column was heated to 10 ° C / min. The acquisition of mass was 10-800 AMU. The spectra were reported as m / z (relative abundance).

Example 1 3,3, 3-Trifluoropropyl- (2-trimethylsilylpiperidinyl) -dimethoxysilane trimethylsi1iIpiperidinyl-N-tert-butylcarbamate - A 1000 ml flask was charged with piperidinyl-N-tert-butylcarbamate (25.0 g, 135 mmol), tetramethylethylenediamine ("TMEDA", 44 mL, 290 mmol) and anhydrous ether (300 mL). The contents were cooled to -78SC. Sec-butyl lithium (125 mL of 1.3 M solution in cyclohexane, 162 mmol) was added over 25 minutes. The contents were stirred for 3.5 hours while the reaction temperature was maintained at -78BC. Chlorotrimethylsilane ("TMS-C1", 21.0 mL, 165 mmol) was added over 15 minutes and the contents allowed to warm to room temperature and stirred for 18 hours. The solution was poured into dilute hydrochloric acid (400 L, 0.2 N). The layers were separated and the organic layer was washed with 0.2 N HCl (3 x 100 ml) and dried (MgSO4). Removal of solvent through rotary evaporation provided 53.3 g of 2-trimethylsilylpiperidinyl-N-tert-butylcarbamate C? 3H27N02Si (pm = 257.44); Ms: m / z (relative abundance) 200 (18.2), 186 (40.2), 156"(47.7), 128 (26.9), 84 (45.5), 73 (100), 57 (87.3) 2-Trimethylsilylpiperidine - A The 1000 ml flask was charged with 600 ml of ethyl acetate and cooled to 5 [deg.] C. Anhydrous hydrogen chloride (> 99%) was bubbled through the ethylene acetate for 15 minutes. 2-trimethylsilyl-piperidinyl-N-tert-butylcarbamate (107 g, 416 mmol) was added.The solution was stirred for 18 hours.The product was extracted into water (3 x "200 ml), the layers separated, and The combined aqueous layers were washed with ether (200 ml). The aqueous portion was brought to pH 14 using 45% (weight / v) potassium hydroxide and extracted with ether (3 x 150 ml). The combined organic portions were dried (MgSO4) and the solvent was removed by rotary evaporation. Distillation under reduced pressure (bp 29SC, 0.5 mm Hg) provided 2-trimethylsilylpiperidine (17.0 g, 108 mmol, 26% yield, 97.4% purity by GC); CßH? 3NSi (pm = 157.33); rH NMR: (CDC13) a "49.0, 48.4, 27.6.27.0, 26.2, -4.4; IR (capillary film) v 2926, 2851, 1440, 1258, 1247, 918, 888, 833, 765, 737, 696; MS: m / z (relative abundance) 128 (7.5), 85 (100), 73 (13.8), 56 (17.7), 28 (10.1) .3,3, 3-Tri-fluoropropyl (2-trimethyl-1-diol-1-diol) dimethoxysilane A 500 mL round-bottom flask was charged with tetrahydrofuran (300 mL) and isopropylmagnesium chloride (21.5 mL of a 2.0M solution in THF, 43 mmol), the contents were cooled to 15 [deg.] C. 2-trimethylsilylpiperidine (44.5 mmol) for fifteen minutes through the pressure equalization addition funnel The cold bath was separated and the contents were stirred for two hours.3,3-tri-fluoropropyltrimethoxysilane (39.5 mmol) was added. ) through a pressure equalization addition funnel The content was brought to reflux (65-70BC) for two hours, and the progress of the reaction was monitored -by GC.The isolation was achieved by eliminating the THF at Ravés of rotating evaporation, taking the residue in ether (250 m), filtration and removal of ether through rotary evaporation. Purification was achieved by distillation to provide 3,3,3-tri fluoropropyl (2-trimethylsilyl-piperidinyl) dimethoxysilane (33.5 mmol, 85.0% yield). C? 3H28 02SiF3 (mw = 343.53); ? NMR: (CDC13) 3.5 (2, 6H), 3.1-2.9 (m, 1H), 2.8-2.6 (m, 2H), 2.2-2.0 (m, 2H), 1.8-1.35 (m, 5H), 1.32 -1.15 (m, 1H), 0.9-0.7 (, 2H), 0.1 (s, 9H); 13C NMR: (CDC13) 127.7 (quartet J = 275 Hz), 50.1, 42.6, 42.2, 28.0 (quartet J = 30 Hz), 27.8, 23.4, 3.0, 0.2, -4.2; MS: m / z (relative abundance) 328 (1.2), 270 (100), 246 (2.2), 155 (6.5), 125 (12.0), 84 (21.5).Example II 3-Trimethylsilyl-1-pyrrolidinyl-N-tert-butylcarbamate of 3,3,3-tri fluoropropyl) 2-trimethylsilylpyrrolidinyl) -dimethoxysilane - A 1000 mL flask was charged with pyrrolidinyl-N-tert-butylcarbamate (23.2 g, 136 mmol) , tetramethylethylenediamine (44 mL, 290 mmol) and anhydrous ether (300 mL), and cooled to -78 ° C. Sert-butyl lithium (125 mL of 1.3M solution in cyclohexane, 162 mmol) was added over 25 minutes. The reaction contents were stirred for 3.5 hours while maintaining the temperature at -78 ° C. Chlorotrimethylsilane (21.0 mL, 165 mmol) was added over 15 minutes. The contents were allowed to warm to room temperature and were stirred for 18 hours. The solution was poured into dilute hydrochloric acid (750 mL, 0.2 N HCl). The layers were separated and the organic layer was washed with 0.2 N HCl (3 x 200 mL), brine (1 x 250 mL), and dried (MgSO4). Removal of solvent through rotary evaporation gave 93 g of crude product. Distillation under reduced pressure (85-92sC, 1.8 mm Hg) provided 45.9 g (189 mmol, 70% yield) of 2-trimethylsilyl-pyrrolidinyl-N-tert-butylcarbamate; C? 2H25N02Si (mw = 243.42). 2-Trimethylsilylpyrrolidine - A 1000 L flask was charged with 600 mL of ethyl acetate and cooled to 5SC. Anhydrous hydrogen chloride gas (99 +%) was bubbled through ethyl acetate for 15 minutes. The HCl feed was stopped, the ice bath was separated, and 2-trimethylsilyl pyrrolidinyl-N-tert-butylcarbamate (45.9 g, 189 mmol) was added. The solution was allowed to stir for 18 hours. Water (250 mL) was added to the solution. The layers were separated and the product was extracted into water (3 x 200 L). The aqueous portion was adjusted to pH 14 using 45% (w / v) of potassium hydroxide. Ether (200 mL) was added, the layers were separated, and the aqueous layer was extracted into ether (3 x 150 mL). The combined organic portions were dried (MgSO4) and the solvent was removed by rotary evaporation. Distillation under reduced pressure (25SC, 1.5 mm Hg) provided 2-trimethylsilylpyrrolidine (16.0 g, 112 mmol, 64% yield,> 99% purity); d7Hn Si (mw = 143.30); 13C NMR: 49.0, 48.9, 28.1, 26.7, -3.3, -3.6, -4.0; IR (capillary film) v 2952, 2866, 2823, 2752, 1423, 1247, 1069, 936, 892, 837, 747, 692, 622; MS: m / z (relative abundance) 115 (11.9), 100 (14.9), 73 (10.0), 70 (100), 43 (12.4), 28 (13.2), 3.3, 3-Trifluoropropyl 2- rimetiIsi1i 1pyrrolidinyl) dimethoxysilane - A 500 mL round bottom flask was charged with tetrahydrofuran (300 mL) and isopropylmagnesium chloride (28.25 L of a 2.0 M solution in THF, 56.5 mmol). The contents were cooled to 152C. 2-Trimethylsilylpyrrolidine (58.0 mmol) was added over fifteen minutes through a pressure equalization addition funnel. The cold bath was separated and the contents were stirred for two hours. 3, 3, 3-Trifluoropropyltrimethoxysilane (51.3 mmol) was added via pressure equalization addition funnel. The contents were taken. at reflux (65-70sC) for two hours, and the progress of the reaction was monitored by GC. Isolation was achieved by removing the THF through rotary evaporation, taking the residue in ether 8250 L), filtering and removing ether through rotary evaporation. Purification was achieved by distillation to provide 3,3,3-tri fluoropropyl (2-trimethylsilylpyrrolidinyl) dimethoxysilane (46.7 mmol, 91% yield). C12H26N02Si2F3 (mw = 329.51); ? NMR: (CDC13) 3.50 (2, 3H, 3.45 (s, 3H), 3.25-3.10 (m, 1H), 2.90-2.80 (m, 1H), 2.80-2.65 (m, 1H), 2.20-1.50 (m , 6H), 0.85-0.75 (m 2H), -0.05 (s, 9H), 13C NMR: (CDC13) J 129.6 (quartet J = 275), 50.1, 49.0, 47.6, 46.7, 28.2 (quartet J = 30 ), 28.0, 27.5, 2.9, -2.7; 29Si NMR: (CDC13) 2.07, -34.74; MS: m / z (relative abundance) 314 (1.5), 256 (100), 232 (1.7), 155 (3, 8), 125 (3.6) 70 (4.2).

Example III (3- (3-Methyl feryl) piperidinyl) -N-er-butylcarbamate of 3,3,3-trifluoropropyl) 2- (3-methylphenyl) -piperidin-nyl) dimethoxysilane - A 500 mL flask was charged with piperidinyl-N-tert-butylcarbamate (18.5 g, 100 x 102 mmol), tetramethylethylenediamine (33 mL, 220 mmol), and THF (200 mL). The contents were cooled to -78SC. Secon-butyl lithium (93 mL of 1.3 M solution in cyclohexane, 120 mmol) was added over 15 minutes. The reaction was stirred at -78 ° C for 3.5 hours. A 1000 mL flask was charged with THF (200 L), 3-iodotoluene (25.7 mL, 2.00 x 102 mmol), copper cyanide (I) (0.896 g, 1.00 x 102 mmol), and bis (tri-phenyl) chloride. phosphine) palladium (3.5 g, 5.0 mmol). The contents were cooled to -782C. The piperidinyl-N-tert-butylcarbamate anion was transferred to the iodotoluene solution via cannula. The reaction was allowed to stir for 18 hours and then heated to reflux (75aC) for another 18 hours. The cooled contents were added to water (20.0 mL), the layers separated, and the aqueous layer extracted with ether (2 x 150 mL). The combined organic portions were washed with brine 83 x 150 mL) and dried (MgSO 4). Removal of solvent by rotary evaporation afforded 59.5 g of crude 2- (3-methyl-phenyl) -piperidinium-N-tert-butylcarbamate. C17H25N02 (mw = 275.39); MS: m / z (relative abundance) 275 (0.3), 219 (73.0), 202 (12.4), 174 (97.3), 158 (34.8), 146 (20.6), 132 (14.6), 57 ( 100). 2- (3-Methyl phenyl) piperidine - A 1000 L flask was charged with ethyl acetate (600 L) and cooled to 52C. Anhydrous hydrogen chloride gas (99%) was bubbled through ethyl acetate for 15 minutes. The HCl feed was stopped, the ice bath was separated, and 2- (3-methyl phenyl) piperidinyl-N-tert-butylcarbamate (59.5 g, 216 mmol) was added. The solution was allowed to stir for 18 hours. Water (250 mL) was added to the solution. The layers were separated and the product was extracted into water (3 x 200 mL). The aqueous portion was adjusted to pH 14 with 45% (weight / v) potassium hydroxide. The product was extracted into ether (4 x 150 L). The combined organic portions were dried (MgSO4) and the solvent was removed by rotary evaporation. Distillation under reduced pressure (75-90aC, 03. mm Hg) yielded 2- (3-methylphenyl) piperidine (10.4 g, 59.3 mmol, 27.5% yield); C? 2H? 7N (mw = 175.27); ? NMR: (CDC13) 7.2-7.0 (m, 4H), 3.5 (m, 1H), 3.1 (m, 1H), 3.7 (t, 1H), 2.3 (s, 3H), 1.9-1.4 (, 7H) ): 13C NMR: (CDC13) 145.4, 137.6, 128.0, 127.5, 127.0, 123.5, 62.1, 47.6, 34.8, 25.6, 25.3, - 21.1; IR (capillary film) v 3319, 3267, 3022, 2924, 1932, 1855, 1777, 1680 1441, 1323, 1108, 783, 701; MS: m / z (relative abundance) 175 (35.7), 160 (10.4), 146 (45.0), 143 (34.6), 118 (100). 91 (31.7) 84 (48.4), 56 (7.7), 28 (23.3). 3,3, 3-Trifluoropropyl f 2- (3-methyl phenyl) piperidinyl) dimethoxysi lano - A 500 mL round bottom flask was charged with tetrahydrofuran (300 mL) and isopropylmagnesium chloride (15 mL of a 2.0 solution. M in THF, 30 mmol). The contents were cooled to 15SC. 2- (3-methyl phenyl) piperidine (34.3 mmol) was added for fifteen minutes through the pressure equalization addition funnel. The cold bath was separated and the contents were stirred for two hours. It was added 3, 3, 3-tri-fluoropropyl trimethoxysilane (31.1 mmol) through addition funnel of pressure equalization. The contents were brought to reflux (65-70aC) for two hours, and the reaction progress was monitored by GC. Isolation was achieved by eliminating the THF through rotary evaporation, taking the residue in ether (250 mL), filtering and removing ether through rotary evaporation. Purification was achieved by distillation to provide 3, 3, 3-trifluoropropyl (2 - 2 \ (3-methylphenyl) -piperidinyl) dimethoxysilane (24.1 mmol, 80.4% yield, b pt 101? C at 02 mm Hg). C17H26N02SiF3 (mw = 361.47); MS: m / z (relative abundance) 361 (13.4), 332 (3.6), 270 (100), 174 (5.6), 155 (9.1), 125 (12.0), 105 (12.2), -59 (19.4).

Example IV (2- (3-Methyl phenyl) -pyrrolidinyl) -N-tert-but-i-carbamic acid 3,3,3-trifluoropropyl (2- (3-methylphenyl) -pyrroli-dinyl) -dimethoxysilane - A flask was charged of 500 mL with pyrrolidinyl-N-tert-butylcarbamate (17.3 g, 101 mmol), tetramethylethylenediamine (33 mL, 220 mmol), and THF (200 mL). The contents were cooled to -78aC. Secon-butyl lithium (93 mL of 1.3 M solution of cyclohexane, 120 mmol) was added over 15 minutes and the contents were stirred at -78aC for 3.5 hours. A 1000 mL flask was charged with THF (200 mL), 3-iodotoluene (25.7 mL, 7.00 x 102 mmol), copper cyanide (I) (0.896 g, 10.0 mmol), and bis- (tri-phenyl) phosphide. ina) palladium (3.5 g, 5.0 mmol). The contents were cooled to -78 ° C. The piperidinyl-N-tert-butylcarbamate anion was transferred to the solution of iodotoluene through cannula, the reaction was allowed to stir for 18 hours and then heated to reflux (75SC) for 18 hours. They were added to water (200 mL), the layers were separated and the aqueous layer was extracted with ether (2 x 150 mL) The combined organic portions were washed with brine (3 x 150 mL) and dried (MgSO 4). of solvent by rotary evaporation gave 62.5 g of crude product, distillation under reduced pressure (145 [deg.] C., 02. mm Hg) gave 2- (3-methyl-phenyl) pyrrodinyl-N-tert-butylcarbamate (13.3 g, 50.9 g. mmol, 50% yield): C16H23N02 (mw = 261.36) 2- (3-Me-phenyl) pyrrolidene - A 1000 mL flask was charged with ethyl acetate (600 L) and cooled to 5 ° C. Gas was bubbled of anhydrous hydrogen chloride (99% through ethyl acetate for 15 minutes.) The HCl feed was stopped, the Ice bath was removed and 2- (3-methylphenyl) pyrrolidinyl-N-tert-butyl carbamate (35.0 g, 134.mmol) was added. The solution was allowed to stir for 18 hours. Water (250 mL) was added, the layers were separated, and the product was extracted into water (3 X 200 mL). The aqueous portion was adjusted to pH 14 using 45% (w / v) of potassium hydroxide. The product was extracted into ether (4 x 150 mL). The combined organic portions were dried (MgSO4) and the solvent was removed by rotary evaporation. Distillation under reduced pressure (115-122aC, 2 mm Hg) yielded a 70:30 mixture of 2- (3-methyl phenyl) -pyrrolidine and 2- (3-methyl phenyl) pyrrolidene (14 g. performance ) . 2- (3-Methyl phenyl) pyrrolidine - A pressure reactor was charged with the mixture of olefin / product (14 g), absolute ethyl alcohol (140 mL) and platinum oxide (2.8 g, 12 mmol). The reactor was filled with hydrogen (99.99%) at a pressure of 3.52 kg / cm2 manomotive. The reaction mass was stirred for 18 hours during which time the pressure decreased to 0.21 kg / cm 2 gauge. The ethyl alcohol was distilled off under nitrogen. Distillation of the residue under reduced pressure (63-74sC, 0.1 mm Hg) yielded 2- (3-methyl-phenyl) -pyrrolidine (10.8 g, 67 mmol, 77% yield, 97% purity); CuH? 5N (mw = 161.24); ? NMR: (CDC13) 7.3-6.9 (m, 4H), 4.1 (t, 1H), 3.1 (m, 1H), 2.9 (m, 1H), 2.3 (s, 3H), 2.1 (m, 1H), 1.9 (m, 3H), 1.6 (m, 1H); 13C NMR: < J (CDC13) 144.9, 137.9, 128.2, 127.5, 127.2, 123.6, 62.6, 47.0, 34.3, 25.6, 21.4; IR (capillary film) v 3327, 3014, 2953, 2866, -1937, 1861, 1783, 1399, 781, 709, MS: m / z (relative abundance) 160 (62.9), 246 (40.5), 132 (100) , 118 (92.6), 92 (25.2), 70 (45.3), 43 (6.0), 28 (14.8). 3,3, 3-Trifluoropropyl (2- (3-methyl phenyl) pyrrolidinyl) dimethoxysilane - A 500 mL round bottom flask was charged with tetrahydrofuran 8300 mL) and isopropylmagnesium chloride (20 mL of a 2.0 M solution in THF 40 mol). The contents were cooled to 159 C, 2- (3-methylphenyl) pyrrolidine (39.1 mmol) was added for fifteen minutes through the pressure equalization addition funnel. The cold bath was removed and the contents stirred for two hours. 3-3-3-Trifluoro-propyltrimethoxysilane (36.3 mmol) was added through a pressure equalization addition funnel. The contents were brought to reflux (65-70sC) for two hours, and the progress of the reaction was monitored by GC. Isolation was achieved by eliminating the THF through rotary evaporation, taking the residue in ether (250 L), filtration and ether removal through rotary evaporation. Purification was achieved by distillation to provide 3,3,3-trifluoropropyl (2- (3-methyl phenyl) -pyrrolidinyl) dimethoxysilane (24.3 mmol, 62.2% yield). C? 6H24N02SiF3 (mw = 347.45) bp = 128aC at 0.2 mm Hg; ¿? NMR: (CDC13) 7.3-6.9 (m, 4H), 4.5 (t, 1H), 3.41 (s, 3H), 3.40 (s, 3H), 3.3 (t, 2H), 2.3 (s, 3H), 2.2 -2.1 (m, 2H), 2.0-1.7 (m, 4H), 1.7-1.6 (m, 2H); 13C NMR: (CDCla) 147.8, 137.7, 128.1, 127.6 (quartet, J = 275.9"Hz), 127.2, 126.8, 123.2, 61.7, 50. 3, 47.4, 37.0, 34.3, 27.7 (quartet, J = 30.1 Hz) 21. 4, 3.0: MS: m / z (relative abundance) 347 (18.0), 318 (8.3), 304 (3.7), 256 (100), 155 (12.0), 125 (15.9), 59 (24.6).

Example V Cis-2, 6-dimethylpiperidine of 3, 3, 3-tri-fluoro-propyl (cis-2,6-dimeti-1-piperidinyl) dimethoxysilane - A 1000 mL round bottom flask was charged with 5 M KOH (600 mL , 3 moles) and lutidine (15.0 g, 1.50 x 102 mmol). A solid aluminum / nickel alloy was added for 48 hours (1200 g). During the addition of the alloy, gas evolved and the internal temperature increased from 352C to 652C (no more than 15 g of the alloy were added in one portion). The salts were filtered through celite (Note: CAUTION: A solid type flammable Raney nickel remains in the celite.This material will ignite in air if the filter cake dries.The solid is neutralized better by stirring it in a generous amount of nitric acid diluted for 48 hours.), and the filter cake was washed with ether and water. The layers separated. The product was extracted into ether (3 x 150 mL) and dried (MgSO 4), leaving crude 2,6-dimethylpiperidine (8.13 g, 71.2 mmol, 51% yield). 3,3,3-Trifluoropropyl (cis-2,6-dimethylpiperidinyl) dimethoxysiolone-Un. 500 L round bottom flask was charged with tetrahydrofuran (300 mL) and isopropylmagnesium chloride (31 L of a 2.0 M solution in THF, 62 mmol). The contents were cooled to 15 aC. Cis-2,6-dimethylpiperidine (64 mmol) was added for fifteen minutes through the pressure equalization addition funnel. The cold bath was removed and the contents were stirred for two hours. 3, 3, 3-Tri-fluoro-propyltrimethoxysilane (57 mmol) was added via pressure equalization addition funnel. The contents were brought to reflux (65-702C) for two hours, and the reaction progress was monitored by GC. Isolation was achieved by removing the THF through rotary evaporation, taking the residue in ether (250 mL), filtering and removing ether through rotary evaporation. Purification was achieved by distillation to provide 3,3,3-trifluoropropyl (cis-2,6-dimethylpiperidinyl) dimethoxysilane (27.4 mmol, 48% yield). C12H24N02SiF3 (mw = 299.40) for example = 66SC at 0.3 mm Hg; "? NMR: < j- (CDCl3) 3.5 (s, 6H), 3.4-3.3 (m, 2H), 2.2-2.0 (m, 2H), 1.9-1.7 (m, 1H), 1.6-1.4 (m , 5H), 1.2-1.0 (m, 6H), 0.8-0.7 (m, 2H), 13C NMR: (CDC13) or 128 (quartet, J = 275 Hz), 50.1, 44.2, 31.6, 28.3 (quartet, J = 30 Hz), 24.6, 20.5, 14.3: MS: m / z (relative abundance) 299) 0.7), 284 (100), 202) 6.7), 155 (7.9), 98 (12.7), 59 (12.5).

Example VI 3,3, 3-TrifluofopropylKl, 2,3,4-tetrahydroquin-linyl) dimethoxysilane - A 500 mL round bottom flask was charged with tetrahydrofuran (300 L) and isopropylmagnesium chloride (30 mL of a 2.0 solution. M in THF, 60 mmol). The contents were cooled to 15SC. 1, 2, 3, 4-tetrahydroquinoline (60 mmol) was added over fifteen minutes through the pressure equalization addition funnel. The cold bath was removed and the contents were stirred for two hours. 3, 3, 3-Trifluoro-propyltrimethoxysilane ("54.5 mmol) was added through a pressure equalization addition funnel.The contents were brought to reflux (65-70sC) for two hours and the reaction progress was monitored by GC The isolation was achieved by eliminating the THF through rotary evaporation, taking the residue in ether (250 mL), filtering and removing ether through rotary evaporation.The purification was achieved by distillation to provide 3, 3, 3-tri fluoropropyl- (1, 2, 3, 4-tetrahydroquinolinyl) dimethoxysilane (54 mmol, 99% yield) CHH20NO2SiF3 (mw = 319.39) bp = 110SC at 0.35 mm Hg;? NMR: (CDC13) 7.1-6.4 (m , 4H), 3.6-3.2 (m, overlap with single, 8H), 2.9-2.7 (m, 2H), 2.2-1.7 (m, 4H), 1.3-0.7 (m, 2H); 13C NMR : (CDCl,) ^ 130.2, 129.6, 128 (quartet, J = 275 Hz), 126.8, 126.5, 119.2, 117.0, 50.5, 43.5, 27.8 (quartet, J = 30 Hz), 23.8, 22.4, 3.4; MS: m / z (relative abundance) 319 (100), 222 (11.7), 190 (6.5), 182 (6.2) 155 (10.7), 132 (55.0), 125 (21.8), 117 (12.1), 59 (32.6).

Example VII 3.3, 3-Tri fluoropropyl (1, 2,3,4-tetrahydroisoqui-nolinyl) dimethoxysilane - A 500 mL round bottom flask was charged with tetrahydrofuran (300 mL) and isopropylmagnesium chloride (30 mL of? a solution at 2.0 M in THF, 60 mmol). The contents were cooled to 152C. 1, 2, 3, -tetrahydrosikinoline (60 mmol) was added for fifteen minutes through the pressure equalizing addition funnel. The cold bath was removed and the contents were stirred for two hours. 3, 3, 3-Tri fluoropropyl trimethoxysilane (54.5 mmol) was added via pressure equalization addition funnel. The contents were brought to reflux (65-70aC) for two hours and the reaction progress was monitored by GC. The isolation was achieved by eliminating the THF through rotary evaporation, taking the residue in ether (250 mL), filtration and ether removal through rotary evaporation. The purification was achieved by distillation to provide 3, 3, 3-tri fluoropropyl) -1, 2, 3, 4-tetrahydroisoquinolinyl) dimethoxysilane (54 mmol, 99% yield). C14H20NO2SiF3 (mw = 319.39) pb = 98aC at 0.3 mm Hg; ? NMR: (CDC13) 7.2-6.9 (m, 4H), 4.2-4.0 (d, 2H), 3.6-3.4 (s, 6H), 3.3-3.1 (dt, 2H), 2.8-2.6 (m, 2H) ), 2.2-1.9 (m, 2H), 0.9-0.8 (m, 2H); 13C NMR: (CDC13) 135.9, 135.1, 129.4, 128 (quartet J = 275 Hz), 126.0, 125.9, 125.8, 50.4, 46.5, 42.1, 29.9, 28 (quartet, J = 30 Hzj, 2.8, MS: m / z (relative abundance) 319 (38.3), 318 (100), 222 (7.9), 132 (21.0), 104 (21.4), 79 (9.8), 59 (13.4).

Example VIII 3.3, 3-Tri fluoropropyl (decahydroquinolinyl) di-methoxysilane - A 500 mL round bottom flask was charged with tetrahydrofuran (300 mL) and isopropylmagnesium chloride (28.75 mL of a 2.0 M solution in THF, 57.5 mmol). The contents were cooled to 15 aC. Decahydroquinoline (57.5 mmol) was added for fifteen minutes through the pressure equalization addition funnel. The cold bath was removed and the contents were stirred for two hours. 3, 3, 3-Trifluoropropyltrimethoxysilane (52.3 mmol) was added via addition equalization funnel. The contents were brought to reflux (65-702C) for two hours, and the reaction progress was monitored by GC. Isolation was achieved by stirring the THF through rotary evaporation, taking the residue in ether (250 mL), filtration and ether removal through rotary evaporation. Purification was achieved by distillation to provide 3, 3, 3-tri. fluoropropyl (deca-hydroquinoliuyl (dimethoxysilane (53.1 mmol, quantitative yield) d4H26N02SiF3 (mw = 325.44) bp = 103BC at 1.0 mm Hg;? NMR: (CDCl3) /3.5 (s, 6H), 3.1-2.7 (m, 3H), 2.2-1.9 (m, 3H), 1.8-1.1 (m, 12H), 0.9-0.7 (m, 2H), 13C NMR (CDC13) 127.9 (quartet, J = 275 Hz), 52.6, 50.4, 38.2 , 36.9, 29.0, 28.5, 27.8 (quartet, J = 30 Hz), 26.4, 26.3, 20.5, 3.1, MS: m / z (relative abundance) 325 (14.3), 282 (100), 228 (4.1), 125 (6.8), 96 (11.3), 59 (12.6).

Example IX 3.3, 3-Trifluoropropyl (bis (2-ethylhexy1) amino-dimethoxysilane - A 500 mL round bottom flask was charged with tetrahydrofuran (300 mL) and isopropylmagnesium chloride 825 mL of a 2.0 M solution in THF 50 mmol). The contents were cooled to 15 ° C., Bis (2-ethylhexyl) amine (50 mmol) was added for fifteen minutes through the pressure equalization addition funnel. The cold bath was removed and the contents were stirred for two hours. 3, 3, 3-Tri fluoropropyltrimethoxysilane (45 mmol) was added via pressure equalization addition funnel. The contents were brought to reflux (65-70sC) for two hours, and the reaction progress was monitored by GC. The isolation was achieved by removing the THF through rotary evaporation, taking the residue in ether 8250 mL), filtration and removal of ether through rotary evaporation. Purification was achieved by distillation to provide 3,3,3-trifluoropropy 1-bis (2-ethylhexyl) amino-dimethoxysilane (44 mmol, 98% yield). C21H44N02SiF3 (mw = 427.66) pb = 200SC at 1. mm Hg; ? NMR: (CDCl3) < f 3.5 (s, H), 2.6-2.4 (dd, 4H), 2.2-2.0 (, 2H), 1.6.1.1 (m, 18H), 1.0-0.7 (m, 14H); "C NMR: (CDC13) ^ 128 (quartet, J = 275 Hz), 50.4, 48.5, 39.4, 36.9, 30.8, 29.1, 28.2 (quartet, J = 30 Hz), 23.2, 14.2, 10.3, 3.2 MS: m / z (relative abundance) 328 (100), 230 (25.6), 155 (7.4), 109 (2.9).

Example X Polymerization Process The aminosilane compounds of Examples I-IX were used as electron donors to polymerize propylene monomer. The polymerization reactor was heated to 70 ° C and purged with a slow flow of argon for 1 hour. The reactor was then pressurized to 7.03 kg / cm 2 gauge with argon at 70 ° C and then vented. This procedure was repeated 4 times more. The reactor was then cooled to 30SC. Separately, to an addition funnel purged with argon, were introduced in the following order: 75 mL of hexane, 4.47 mL of solution to 1.5 M of triethylaluminum (TEAL) "(0.764 g, 0.0067 mol) in hexane, approximately 3.4 mL of 0.1 M solution of the aminosilane electron donors (0.00034 mol) of Examples I-IX and allowed to stand for 5 minutes.From this mixture, 35 mL was added to a flask, then, 0.0129 g of FT4S solid catalyst component (a titanium halide and electron donor supported on a catalyst component of active MgCl 2 compound commercially available from Montell Italia SpA) was added to the flask and mixed with stirring for a period of 5 minutes. introduced, under an argon purge, to the above polymerization reactor at room temperature The remaining hexane / TEAL / silane solution was then drained from the addition funnel into the flask, the flask watered and drained to the reactor and the injection valve was closed. The reactor of polymerization was slowly charged with 2.2 L of liquid propylene, while stirring, and 0.25 mole percent of H2. then the reactor was heated to 70 ° C and the polymerization was started for about 2 hours at constant temperature and pressure. After about 2 hours the stirring was stopped and the remaining propylene was slowly vented. The reactor was heated to 802C, purged with argon for 10 minutes and then cooled to room temperature and opened. The polymer was removed and dried in a vacuum oven at 80 aC for 1 hour before the test was performed. unless otherwise specified, the intrinsic viscosity of the polymers, IV; is measured in decalin at 135QC using a type viscometer tube Ubbelohde by the method of J. H. Elliot et al., J.

Applied Polymer Sci., 14, 2947-63 (1970). The polymer illage is calculated according to the formula: mileage = grams of polypropylene grams of catalyst The percent of xylene solubles at room temperature,% XSRT, of the polymer was determined by dissolving 2 g of polymer in 200 ml of xylene at 135SC, cooling in a constant temperature bath at 22aC and filtering through fast filter paper. An aliquot of the filtrate was evaporated to dryness, the residue was weighed and the wt% of the soluble fraction was calculated. The test results are exposed in the Table 1 below.

Table 1 Aminosilane Hydrogen "Millax e Viscosity Intrin% (g pp / g cat) dry (dL / g) 0 22, 353 4.94 0.2 47.168 3.7 Example 1 0.75 57.767 2.63 1.5 56, 86 1.83 2.5 55.208 1.57 5 54, 222 1.16 0 21, 329 9.4 0.2 45.487 3.48 Example II 0.75 57, 714 2.4 1, 5 54, 528 1.82 2.5 53, 555 1.48 5 56, 163 1.25 0 19, 805 6.47 0.2 43, 750 2.39 Example III 0.75 51.386 1.56 1-5 46, 818 1.22 2.5 43, 297 1.01 0 20, 952 11.1 0.2 47, 211 2.78 Example IV 0.75 52.444 1.95 1.5 49.285 1.54 2.5 46, 333 1.22 5 42, 755 0.91 Table 1 (continued) Aminosilane Flow Regime XSRT P.I. of Fusion (% by weight) 0 '2.19 0.56 3.03 5.6 Example 1 3.18 1.93 12.49 2.57 4.5 31.27 2.31 4. 6 98.89 2.6 4.6 0. 02 2.79 0.75 2.21 5.5 Example II 4.29 2.18 12.66"2.47 5.2 34.54 .79 4.9 96.27 2.75 4.6 0. 01 3.39 4.3 2.45 5.0 Example III 25.23 2.24 88.09 2.74 4. 4 213.06 2.86 4.4 0. 01 3.43 1.6 2.1 4.8 Example IV 9.03 2.42 30.43 2.42 4.5 77.65 2.15 4.4 307.31 2.85 4.5 Aminosilane Hydrogen Mileage Viscosity Intrin-% (g pp / g cat) dry (dL / g) 0 14.601 7.72 0. 2 33, 465 2.28 Example V 0. 75 41, 456 1.58 1,, 5 42, 391 1.26 2. .5 42, 173 1.11 0 18, 216 6, .12 0.2 45,398 2 .04 Example VI 0.75 54,857 1, 5 1.5 46, 923 2.5 48, 620 5 42,058 0 17, 939 6.88 0.2 37, 804 2.05 Example VII 0.75 44, 151 1.47 1.5 37, 378 2.5 39.754 5 36.090 0 19, 000 10.23 Example VIII 0.2 40.280 2.57 0.75 47.407 1.93 Aminosilane Hydrogen Mileage Viscosity Intrin- / o (g pp / g cat) dry (dL / g: 0 19,655 5.16 0.2 36, 272 2.08 Example IX 0.75 40.540 1.21 1.5 38, 867 2.5 36.581 5 33, 966 Aminosilane R Régéggiimmeenn de F Fyuujjoo X XSSRRTT P.I. of Fus; Lón (% by weight 0.03 5.15 5.04 3.5 6.6 Example V 25.3 2.87 75.3 2.95 4.5 153.6 3 4.7 0. 03 4.49 6.82 2.85 4.5 Example VI 29.56 2.77 74.7 2.94 4.3 96.4 2.85 4.3 551 2.97 4.4 Aminosilane Flow Regime XSRT P.I. of Fusion (% by weight) 0.03 3.37 14.2 2.55 4.4 Example VII 32.63 2.45 101.4 2.64 4.3 149.3 2.41 4.3 694.8 2.83 4.2 0. 01 2.95 Example VIII 2.77 2.15 N.D. * 11.75 2.2 0. 11 8.27 13.24 7.29 4.4 Example IX 75 5.94 179.1 5.86 4.6 344.4 8.48 4.5 1,598 6.55 4.4 EXAMPLE OF COMPARISON The polymerization procedure of Example X was followed, using 0.25% hydrogen and a ratio of 20/1 Al / Si, and with 3,3,3-tri fluoropropyl (4-methyl-piperidyl) dimethoxysilane used as the aminosilane. - 4( The catalyst exhibited a mileage of 43.900 grams of polypropylene per gram of catalyst. The resulting polymer had an intrinsic viscosity of 2.35, an XSRT of 1.51% and a polydispersity index of 4.22. Other features, advantages and embodiments of the invention described herein will be readily apparent to those who exercise ordinary experience following the above exposures. In this regard, even when specific embodiments have been described in considerable detail, variations and modifications of these embodiments may be made without departing from the spirit and scope of the invention as described and claimed.

Claims (15)

1. CLAIMS 1. - An aminosilane of the following formula R2 wherein Ri is a linear or branched Cl-22 alkyl or C3-22 cycloalkyl, which may be substituted with at least one halogen atom; R2 is a bis (linear or branched C1-22 alkyl or cycloalkyl) amino of C3-22, a substituted piperidinyl, a substituted pyrrolidinyl, decahydroquinolinyl, 1, 2, 3, 4-tetrahydroquinolinyl or 1, 2, 3, 4- tetrahydroisoqui-nolinyl, with the substituent selected from the group consisting of linear or branched C? -8 alkyl, phenyl, phenyl and trimethylsilyl substituted with linear or branched Ci-? alkyl, with the proviso that when the substituent is alkyl of C? -8, there must be at least two such substituent groups present and Rt must contain halogen; and R3 is linear or branched C? .B alkyl or C3-8 cycloalkyl.
2. 2. The aminosilane of claim 1, wherein Rx is 3,3,3-trifluoro-propyl.
3. 3. The aminosilane of claim 2, wherein R3 is methyl or ethyl.
4. 4. The aminosilane of claim 3, wherein R2 is bis (linear or branched C1-22 alkyl or cycloalkyl Jaraino of C3-22, 5. The aminosilane of claim 4, wherein R2 is bis (2- ethylhexyl) amino 6. The aminosilane of claim 3, wherein R2 is decahydroquinolinyl 7. The aminosilane of claim 3, wherein R2 is 1, 2, 3, 4-tetrahydro-quinolinyl. Aminosilane of claim 3, wherein R2 is 1, 2, 3, 4-tetrahydro-isoquinolinyl 9. The aminosilane of claim 3, wherein R2 is 2-trimethylsilyl-piperidinyl 10.- The aminosilane of claim 3, wherein R2 is 2- (3-methyl phenyl) piperidinyl 11. The aminosilane of claim 3, wherein R2 is cis-2,6-dimethyl-piperidinyl 12. The aminosilane of claim 3, wherein R2 is 2-trimethylsilyl pyrrolidinyl. 13. - The aminosilane of claim 3, wherein R2 is 2- (3-methyl phenyl) pyrrolidinyl. 14. A catalyst for the polymerization of olefins, comprising the reaction product of: (A) an alkyl aluminum compound; (B) an aminosilane compound of the formula OR3 R2 wherein Ri is linear or branched C1-22 alkyl or C3-22 cycloalkyl, which may be substituted with at least one halogen atom; R2 is bis (linear or branched C? -22 alkyl or cycloalkyl) amino of C3-22, a substituted piperidinyl, a substituted pyrrolidinyl, decahydroquinolinyl, 1, 2, 3, 4-tetrahydroquinolinyl or 1, 2, 3, 4-tetrahydroisoqui-nolinyl, with the substituent selected from the group consisting of C? -8 alkyl, phenyl, phenyl and trimethylsilyl substituted with linear or branched C? -B alkyl, with the proviso that when the substituent is alkyl of C? -8, there must be at least two such substituent groups present and Ri must contain halogen; and R3 is linear or branched C? -a alkyl or C3-22 cycloalkyl; and (C) a solid component comprising a titanium compound having at least one titanium-halogen bond and an electron donor, both supported on an activated anhydrous magnesium dihalide. 15. The catalyst of claim 14, wherein the alkyl aluminum compound is triethylaluminum, and the solid component comprises the reaction product of titanium tetrachloride, active magnesium chloride and an electron donor. SUMMARY OF THE INVENTION An aminosilane of the formula OR3 R2 wherein Ri is linear or branched C1-22 alkyl or C3-22 cycloalkyl, which may be substituted with at least one halogen atom; R2 is a bis (linear or branched C1-22 alkyl or cycloalkyl) amino of C3-22, a substituted piperidinyl, a substituted pyrrolidinyl, decahydroquinolinyl, 1, 2, 3, 4-tetrahydroquinolinyl or 1, 2, 3, 4- tetrahydroisoquinolinyl, with the substituent selected from the group consisting of C 1-8 alkyl, phenyl and trimethylsilyl substituted with linear or branched alkyl of C? -8, with the proviso that when the substituent is C? _8 alkyl, it must be there are at least two such substituent groups present and Rt must contain halogen; and R3 is linear or branched C? -8 alkyl or C3-8 cycloalkyl. The aminosilane can be reacted with an aluminum-alkyl compound and a solid component comprising a titanium compound having at least one titanium-halogen bond and an electron donor, both supported on an activated anhydrous magnesium dihalide, to form a catalyst for the polymerization of olefins.