DE19727065A1 - Low crystallinity polypropylene used for mouldings or films - Google Patents

Abstract

Polypropylene resins with the following properties are new: (1) melt flow ratio of 0.1-1000 g/10 minutes (at 23 deg C and 2.16 kg) ; (2) xylene solubility of 0.5-5 wt.% (at 23 deg C) ; (3) endothermic maximum m.pt. of 153-163 deg C measured by DSC ; (4) 0.01-3 wt.% eluated amount at a temperature below 80 deg C measured by cross-fractionation chromatography (CFC) ; and (5) isotactic Pentad-fraction (mmmm) of 92-98 wt.% measured by <13>C-NMR. The preparation of these resins is also claimed.

Description

The present invention relates generally to a propylene resin. The invention relates in particular on a low crystallinity propylene resin that has specific physical properties and regarding Transparency, flexibility and impact resistance are excellent is.

Crystalline polypropylenes have so far become industrial produced and in terms of their characteristics, such as e.g. B. high crystallinity and high stereoregularity they in different fields, such as B. in motor vehicles and household electrical appliances. Against amorphous polypropylenes, d. H. atactic polypropylenes usually as by-products for which there is no use there, eliminated. However, such amorphous ones Polypropylene in some areas in recent years Found use, e.g. B. in adhesives. Also have Low crystallinity polypropylenes Intermediates between the above crystalline and amorphous polypropylenes, e.g. B. Polypropylene, the one low endothermic peak temperature (Tmp) and one have low isotactic pentad fraction (mmmm) in Excellent compared to highly crystalline polypropylenes Flexibility, transparency and impact resistance. With regard Such propylenes are based on these characteristics  lower crystallinity uses that differ from those distinguish highly crystalline polypropylenes. This means, such low crystallinity polypropylenes become Production of films, foils, etc. used and found Used in injection molding, extrusion, etc. Conventional Low crystallinity polypropylene resins contain Mixture of an amorphous polypropylene resin or one Polypropylene resin with very low crystallinity and a relatively highly crystalline polypropylene resin. If such resins are formed into a film, the amorphous tends Polypropylene component easily from the film bleed out, making the surface of the film sticky. In addition, the highly crystalline polypropylene resin Component to provide a molding that is inadequate Has flexibility and transparency. So it was difficult a polypropylene resin with low crystallinity get that a sufficient level of flexibility and Has transparency and that deliver a non-sticky molded part can.

It is therefore an object of the present invention to to eliminate the above problems and one Low crystallinity polypropylene resin provide that increased flexibility, transparency and has impact resistance, and it's a non-sticky one Can provide molding.

The inventors of the present invention have now found that the above task by a Polypropylene resin, which is a combination of special has physical properties, can be solved.

Thus, the present invention provides a polypropylene resin ready, which has the following physical properties:

• (1) a fluidity (MFR) of 0.1 to 1000 g / 10 min, measured at 230 ° C under a load of 2.16 kg;
• (2) xylene solubility (CXS) of 0.5 to 5.0 at 23 ° C % By weight;
• (3) a peak endothermic temperature (Tmp) of 153-163 ° C, as determined on a melting curve, which with a differential scanning calorimeter (DSC) was measured;
• (4) an eluted amount at a temperature below 80 ° C from 0.01 to 3.0% by weight, measured with a Cross Fractionation Chromatograph (CFC); and
• (5) an isotactic pentad fraction (mmmm) from 92.0 to 98.0% by weight as measured by 13 C-NMR.

The present invention also provides a method for Manufacture of the above polypropylene resin ready which includes the step of polymerizing propylene in Presence of a catalyst comprising the combination contains the following components (A), (B) and (C):

Component (A): a solid catalyst component obtained by contacting a component (A1) which is a solid component containing titanium, magnesium and a halogen as essential components with a component (A2) which is a component made of a silicon compound represented by the general formula R¹R² _3-m Si (OR³) _m (in which R¹ is a branched chain aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group; R² is a hydrocarbon group that is the same as or different from R¹ or a hydrocarbon group containing a hetero atom R³ is a hydrocarbon group having two or more carbon atoms and is represented by 1 m 3); is obtained;
Component (B): an organoaluminum compound component;
Component (C): a component made of a silicon compound represented by the general formula R⁴ _4-n Si (OR⁵) _n (in which R⁴ is a hydrocarbon group, R⁵ is a hydrocarbon group having 2 or more carbon atoms, and 1 n 4) .

Detailed description of the invention Polypropylene resin

The polypropylene of the present invention is characterized by the characterized the following physical properties.

The flowability MFR is in the range of 0.1 to 1000 g / 10 min, preferably from 0.1 to 100 g / 10 min, more preferably from 0.5 to 50 g / 10 min.

If the MFR is below the above range, it is Formability of the polypropylene resin into a film or the like bad, and if the flowability MFR the exceeds the above range, the strength is one Product, such as B. a film deteriorates.

The xylene solubility (CXS) at 23 ° C is in the range of 0.5 to 5% by weight, preferably from 1.0 to 4.0% by weight. If if it exceeds 5% by weight, the film formed tends slightly  to be sticky and if it is less than 0.5% by weight is, the formability into a film is poor.

The main endothermic peak temperature (Tmp) on one Melting curve by using a differential Scanning calorimeter (DSC) is within the range between 153-163 ° C. When the peak temperature is higher than 163 ° C is, the crystallinity is too high to achieve the desired To obtain low crystallinity polypropylene, and if the peak temperature is lower than 153 ° C, the Xylene solubility (CXS) too high. The endothermic Main peak temperature is preferably in the range of 157-161 ° C.

The Cross Fractionation Chromatograph (CFC) is for Investigation of the crystallinity distribution of a polymer usable. Using o-dichlorobenzene as Solvent, is the amount eluted at a temperature below 80 ° C in the range of 0.1 to 3.0 wt .-%, preferably from 0.1 to 2.5% by weight.

The eluate at a temperature below 80 ° C corresponds to that so-called amorphous atactic polypropylene. If the eluted amount of it is too large, the molded film be sticky.

The isotactic Pentad fraction (mmmm) measured by 13 C-NMR is in the range of 92.0 to 98.0%, preferably of 92.5 to 97.0%, more preferably from 93.0 to 96.5%.

If the fraction is too high, the crystallinity is too high to the desired polypropylene resin with lower Maintain crystallinity and if the fraction is too low is, in turn, it is not possible to achieve the desired  To obtain polypropylene resin with low crystallinity because of the presence of atactic Polypropylene. The polypropylene resin with lower Crystallinity according to the present invention thus becomes due to its low temperature below 80 ° C in Characterized CFC eluted amount, although there is one has lower crystallinity than conventionally known ones Propylene resins.

Manufacturing

There is no particular limitation on a method for Production of polypropylene resin with lower Crystallinity according to the present invention. Indeed it will preferably be according to the procedure described below produced.

Thus, the polypropylene resin according to the invention low crystallinity preferably by that Polymerization of propylene using a Catalyst, which is the combination of the following components (A), (B) and (C) contains. If desired, can the catalyst is also another component, i. H. the fourth component, in addition to components (A), (B) and (C) included.

Component (A): a solid catalyst component obtained by contacting a component (A1) which is a solid component containing titanium, magnesium and a halogen as essential components with a component (A2) which is a component made of a silicon compound represented by the general formula R¹R² _3-m Si (OR³) _m (in which R¹ is a branched chain aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group; R² is a hydrocarbon group that is the same as or different from R¹ or one containing a hetero atom Is hydrocarbon group; R³ is a hydrocarbon group having 2 or more carbon atoms and is represented by 1 m 3);
Component B: an organoaluminum compound component;
Component C: a component made of a silicon compound represented by the general formula R⁴ _4-n Si (OR⁵) _n (in which R⁴ is a hydrocarbon group, R⁵ is a hydrocarbon group having 2 or more carbon atoms, and 1 n 4).

(1) Solid catalyst component

Component (A) of the catalyst of the present Invention is a product created by contact between one specific solid component (component (A1)) and one specific silicon compound (component (A2)) obtained becomes. If desired, component (A) can present invention in addition to the above three essential components also contain other components.

Component (A1)

The solid component of the present invention is one solid component for stereospecific polymerization of propylene, the titanium, magnesium and halogen as contains essential components. The fixed component can if desired, in addition to the three essential elements contain other elements. The in the fixed Elements contained in the component can be in the form of a  There is a connection. Furthermore, the elements be mutually connected.

Solid components, the titanium, magnesium and halogen are known per se and are described, for example, in Japanese Patent Laid-Open No. 53-45688, 54-3894, 54-31092, 54-39483, 54-94591, 54-118484, 54-131589, 55-75411, 55-90510, 55-90511, 55-127405, 55-147507, 55-155003, 56-18609, 56-70005, 56-72001, 56-86905, 56-90807, 56-155206, 57-3803, 57-34103, 57-92007, 57-1 21003, 58-5309, 58-5310, 58-5311, 58-8706, 58-27732, 58-32604, 58-32605, 58-67703, 58-117206, 58-127708, 58-183708, 58-183709, 59-149905, 59-149906 and 63-108008 known. Of these well-known fixed Components can be any in the present invention be used.

Magnesium compounds serving as a magnesium source may include the following: magnesium dihalide, dialkoxy magnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkyl magnesium, magnesium oxide, magnesium hydroxide, carboxylic acid salts of magnesium, etc. The magnesium compounds are preferably those characterized by Mg (OR⁶) _2-p X _p (in which R⁶ is a hydrocarbon group, the carbon number of which is preferably 1 to 10, X is a halogen and 0 p 2) is represented, for. B. magnesium dihalide and dialkoxy magnesium.

Titanium compounds serving as a titanium source can be those compounds represented by the general formula Ti (OR⁷) _4-q X _q (where R⁷ is a hydrocarbon group, the carbon number of which is preferably 1 to 10; X is a halogen, and 0 q 4 ) being represented. Specifically, the titanium compounds can include the following: TiCl₄, TiBr₄, Ti (OC₂H₅) Cl₃, Ti (OC₂H₅) ₂Cl₂, Ti (OC₂H₅) ₃Cl, Ti (Oi-C₃H₇) Cl₃, Ti (O- n-C₄H₉) Cl₃, Ti ( On-C₄H₉) ₂Cl₂, Ti (OC₂H₅) Br₃, Ti (OC₂H₅) (On- C₄H₉) ₂Cl, Ti (On-C₄H₉) ₃Cl, Ti (OC₆H₅) Cl₃, Ti (Oi-C₄H₉) ₂Cl₂, Ti (O- n -C₅H₁₁) Cl₃, Ti (On-C₆H₁₃) Cl₃, Ti (OC₂H₅) ₄, Ti (On-C₃H₇) ₄, Ti (On- C₄H₉) ₄, Ti (Oi-C₄H₉) ₄, Ti (On-C₆H₁₃) ₄ , Ti (On-C₆H₁₇) ₄ and Ti (OCH₂CH (C₂H₅) C₄H₉) ₄.

In addition, a molecular compound can also be produced by Allowing TiX′₄ (in which X ′ is halogen) to react with one Electron donor, as will be described later, is used as a titanium source. Such Molecular compounds can specifically include the following: TiCl₄ · CH₃COC₂H₅, TiCl₄ · CH₃CO₂C₂H₅, TiCl₄ · C₆H₅NO₂, TiCl₄ · CH₃COCl, TiCl₄ · C₆H₅COCl, TiCl₄ · C₆H₅CO₂C₂H₅, TiCl₄ · ClCOC₂H₅, TiCl₄ · C₄H₄O etc.

In addition, titanium compounds such. B. TiCl₃ (that by reducing TiCl₄ with hydrogen, with Aluminum metal or with an organometallic Compound) can be obtained, TiBr₃, Ti (OC₂H₅) Cl₂, TiCl₂, Dicyclopentadienyltitanium dichloride and Cyclopentadienyltitanium trichloride can be used. Of these Titanium compounds are TiCl₄, Ti (O-n-C₄H₉) ₄ and Ti (OC₂H₅) Cl₃ prefers.

Generally halogen becomes from the above Halogen compounds of magnesium and / or titanium supplied. Alternatively, it can be fed from other halogen sources be, e.g. B. from well-known halogenation agents that Halogen compounds of aluminum, for example AlCl₃, Halogen compounds of silicon, for example SiCl₄, Halogen compounds of phosphorus, for example PCl₃ and PCl₅, halogen compounds from tungsten, for example WCl₆ and halogen compounds of molybdenum, for example MoCl₅ include. The contained in the catalyst component Halogen can be made from fluorine, chlorine, bromine, and iodine  Mixtures of the aforementioned existing group selected will. It is particularly preferably chlorine.

The solid component for use in the present Invention can be in addition to the above essentials Components contain other components, e.g. B. Aluminum components such as Al (OC₂H₅) ₃, Al (O-i-C₃H₇) ₃ and Al (OCH₃) ₂Cl, and boron compounds such as B (OCH₃) ₃, B (OC₂H₅) ₃ and B (OC₆H₅) ₃. These components can be in the solid component remain as aluminum and boron components.

In addition, in the manufacture of the solid Component uses an electron donor as an internal donor will. The electron donors (inner donors) that are used for Production of the solid component can be used may include the following: oxygen-containing Electron donors, e.g. B. alcohols, phenols, ketones, aldehydes, Carboxylic acids, esters of organic or inorganic Acids, ethers, acid amides and acid anhydrides; and Nitrogen-containing electron donors, such as. B. ammonia, Amines, nitriles and isocyanates.

The electron donors can specifically include: (a) alcohols containing 1 to 18 carbons, e.g. B. methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol and isopropylbenzyl alcohol; (b) phenols which contain 6 to 25 carbon atoms and which may contain alkyl groups, e.g. B. phenol, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol and naphthol groups; (c) ketones containing 3 to 15 carbon atoms, e.g. B. acetone, methyl ethyl ketone, methyl isobutyl ketone, acetoketone and benzophenone; (d) aldehydes containing 2 to 15 carbon atoms, e.g. B. acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; (e) Organic acid esters containing 2 to 20 carbon atoms: Monoesters of organic acids, e.g. B. methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octylacetate, cyclohexyl acetate, cellosolv acetate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methylbenzate, ethylbenzate, benzyl, ethylbenzate, benzyl, ethylbenzate, benzyl, ethylbenzate, benzyl, ethylbenzate, benzyl, ethylbenzate, ethylbenzate, benzoate, Phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluylate, ethyl toluylate, amyl toluylate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, α-valerolactone, coumarin and phthalide; and esters of organic polyacids, e.g. B. diethyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl maleate, 1,2-cyclohexane, diethyl carboxylate, ethylene carbonate, norbornane-dienyl-1,2-dimethyl carboxylate, cyclopropane-1,2-dicarboxylic acid-n-hexyl and 1,1-cyclobutane diethyl carboxylate; (f) Esters of inorganic acids comprising silicic acid esters (except silicon compounds represented by the general formula R¹R² _3-m Si (OR³) _m above), e.g. B. ethyl silicate, butyl silicate and phenyltriethoxysilane; (g) acid halides containing 2 to 15 carbon atoms, e.g. B. acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride and isophthaloyl chloride; (h) ethers containing 2 to 20 carbon atoms, e.g. B. methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; (i) amides, e.g. B. acid amides, benzoic acid amide and toluic acid amide; (j) amines, e.g. B. methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethyldiamine; (k) nitriles, e.g. B. acetonitrile, benzonitrile and phenylacetic acid nitrile; (l) alkoxy ester compounds, e.g. B. 2- (ethoxymethyl) ethylbenzoate, 2- (t-butoxymethyl) ethylbenzoate, 3-ethoxy-2-ethylphenyl propionate, 3-ethylethoxypropionate, 3-ethoxy-2-s-ethylbutylpropionate and 3-ethoxy-2-t-ethylbutylpropionate; and (m) ketone ester compounds, e.g. B. 2-ethylbenzoylbenzoate, 2- (4'-methylbenzoyl) ethylbenzoate and 2-benzoyl-4,5-ethyldimethylbenzoate. The electron donors are preferably ester compounds of organic acids and acid halide compounds, more preferably phthalic acid diester compounds, cellosolvacetate ester compounds and phthalic acid dihalides.

Component (A2)

The silicon compound for use in the present invention is represented by a general formula R¹R² _3-m Si (OR³) _m (in which R¹ is a branched chain aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group, R² is a hydrocarbon group that is the same as or different from R¹ , or is a hydrocarbon group containing a hetero atom, R³ is a hydrocarbon group containing 2 or more carbon atoms and 1 m 3). The silicon compound may be a mixture of the silicon compounds represented by the general formula above. When R1 is a branched chain aliphatic hydrocarbon group, the branched chain is preferably branched from a carbon atom adjacent to a silicon atom. The branched chain is preferably an alkyl group, a cycloalkyl group or an aryl group (e.g. a phenyl group or a methyl substituted phenyl group). R1 is preferably a group in which the carbon atom is adjacent to a silicon atom, ie the carbon atom in the α-position is a secondary or tertiary, especially a tertiary carbon atom. When R1 is a branched chain hydrocarbon group, the number of carbon atoms is generally 3 to 20, preferably 4 to 10. When R1 is a cyclic hydrocarbon group, the number of carbon atoms is generally 4 to 20, preferably 5 to 10. R2 is a hydrocarbon group which is the same as or different from R¹, or R² is a hydrocarbon group containing a hetero atom. The number of carbon atoms is generally 1 to 20, preferably 1 to 10. R³ is a hydrocarbon group which has 2 or more carbon atoms and is preferably an aliphatic hydrocarbon group having 2 to 20, preferably 2 to 10, more preferably 2 to 4, carbon atoms .

The silicon compounds for use in the present Invention can specifically include the following: (CH₃) ₃CSi (CH₃) (OC₂H₅) ₂, (CH₃) ₃CSi (CH₃) (O-n-C₃H₇) ₂, (CH₃) ₃CSi (CH₃) (O-i-C₃H₇) ₂, (C₃) ₃CSi (CH₃) (O-n-C₄H₉) ₂, (CH₃) ₃CSi (CH₃) (O-i-C₄H₉) ₂, (CH₃) ₃CSi (CH₃) (O-t-C₄H₉) ₂, (CH₃) ₃CSi (CH₃) ₃CSi (CH₃) (O-n-C₆H₁₃) ₂, (CH₃) ₃CSi (CH₃) (O-n-C₈H₁₇) ₂, (CH₃) ₃CSi (CH₃) (O-n-C₁₀H₂₁) ₂, (CH₃) ₃CSi (C₂H₅) (OC₂H₅) ₂, (CH₃) ₃CSi (n-C₃H₇) (OC₂H₅) ₂, (CH₃) ₃CSi (i-C₃H₇) (OC₂H₅) ₂, (CH₃) ₃CSi (n-C₄H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (i-C₄H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (s-C₄H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (t-C₄H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (n-C₅H₁₁) (OC₂H₅) ₂, (CH₃) ₃CSi (c-C₅H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (n-C₆H₁₃) (OC₂H₅) ₂, (CH₃) ₃CSi (C-C₆H₁₁) (OC₂H₅) ₂, (CH₃) ₃CSi (C₂H₅) (O-n-C₃H₇) ₂, (CH₃) ₃CSi (C₂H₅) (O-i-C₃H₇) ₂, (CH₃) ₃CSi (C₂H₅) (O-n-C₄H₉) ₂, (CH₃) ₃CSi (C₂H₅) (O-i-C₄H₉) ₂, (CH₃) ₃CSi (C₂H₅) (O-s-C₄H₉) ₂,  (CH₃) ₃CSi (C₂H₅) (O-t-C₄H₉) ₂, (CH₃) ₃CSi (C₂H₅) (O-n-C₆H₁₃) ₂, (CH₃) ₃CSi (C₂H₅) (O-n-C₈H₁₇) ₂, (CH₃) ₃CSi (C₂H₅) (O-n-C₁₀H₂₁) ₂, (CH₃) ₃CSi (i-C₃H₇) ₂, (CH₃) ₃CSi (i-C₃H₇) (O-i-C₃H₇) ₂, (CH₃) ₃CSi (i- C₃H₇) (O-n-C₄H₉) ₂, (CH₃) ₃CSi (i-C₃H₇) (O-i-C₄H₉) ₂, (CH₃) ₃CSi (i- C₃H₇) (O-s-C₄H₉) ₂, (CH₃) ₃CSi (i-C₃H₇) (O-t-C₄H₉) ₂, (CH₃) ₃CSi (i- C₃H₇) (O-n-C₆H₁₃) ₂, (CH₃) ₃CSi (i-C₃H₇) (O-n-C₈H₁₇) ₂, (CH₃) ₃CSi (i- C₃H₇) (O-n-C₁₀H₂₁) ₂, (CH₃) ₅CSi (O-n-C₃H₇) (OC₂H₅) ₂, (CH₃) ₃CSi (O-i- C₃H₇) (OC₂H₅) ₂, (CH₃) ₃CSi (O-n-C₄H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (O-i- C₄H₉) (OC₂H₅) ₂, (CH₃) ₂CSi (O-s-C₄H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (O-t- C₄H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (O-n-C₅H₁₁) (OC₂H₅) ₂, (CH₃) ₃CSi (O-c- C₅H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (O-n-C₆H₁₃) (OC₂H₅) ₂, (CH₃) ₃CSi (O-c- C₆H₁₁) (OC₂H₅) ₂, (i-C₃H₇) ₂Si (OC₂H₅) ₂, (i-C₄H₉) ₂Si (OC₂H₅) ₂, (s- C₄H₉) ₂Si (OC₂H₅) ₂, (neo-C₅H₁₁) ₂Si (OC₂H₅) ₂, (c-C₅H₉) ₂Si (OC₂H₅) ₂, (c- C₅H₉) ₂Si (O-n-C₃H₇) ₂, (c-C₅H₉) ₂Si (O-n-C₄H₉) ₂, (c-C₅H₉) ₂Si (O-n- C₅H₁₁) ₂, (c-C₅H₉) ₂Si (O-n-C₈H₁₇) ₂, (c-C₈H₁₁) ₂Si (OC₂H₅) ₂, (c- C₆H₁₁) ₂Si (O-n-C₃H₇) ₂, (c-C₆H₁₁) ₂Si (O-n-C₄H₉) ₃, (c-C₆H₁₁) ₂Si (O-n- C₅H₁₁) ₂, (c-C₆H₁₁) ₂Si (O-n-C₈H₁₇) ₂, (c-C₆H₁₁) Si (CH₃) (OC₂H₅), (c- C₆H₁₁) Si (CH₃) (O-n-C₃H₇) ₂, (c-C₆H₁₁) Si (CH₃) (O-n-C₄H₉) ₂, (c- C₆H₁₁) Si (CH₃) (O-n-C₅H₁₁) ₂, (c-C₆H₁₁) Si (CH₃) (O-n-C₅H₁₇) ₂, (c- C₆H₁₁) Si (C₂H₅) (OC₂H₅) ₂, (c-C₆H₁₁) Si (n-C₄H₉) (OC₂H₅) ₂, (c- C₆H₁₁) Si (C₅H₉) (OC₂H₅) ₂, (C₂H₅) ₃CSi (CH₃) (OC₂H₅) ₂, (C₂H₅) ₃CSi (CH₃) (O-n-C₃H₇) ₂, (C₂H₅) ₂CSi (CH₃) (O-i-C₃H₇) ₂, (C₂H₅) ₃CSi (CH₃) (O-n-C₄H₉) ₂, (C₂H₅) ₃CSi (CH₃) (O-i-C₄H₉) ₂, (C₂H₅) ₃CSi (CH₃) (O-t-C₄H₉) ₂, (C₂H₅) ₃CSi (CH₃) (O-n-C₆H₁₃) ₂, (C₂H₅) CSi (CH₃) (O-n-C₈H₁₇) ₂, (C₂H₅) ₃CSi (CH₃) (O-n-C₁₀H₂₁) ₂, (C₃H₅) ₃CSi (C₂H₅) ₂ (OC₂H₅) ₂, (C₂H₅) ₃Csi (i-C₃H₇) (OC₂H₅) ₂, (C₂H₅) ₃CSi (n-C₄H₉) (OC₂H₅) ₂, (C₂H₅) ₃CSi (i-C₄H₉) (OC₂H₅) ₂, (C₂H₅) ₃CSi (s-C₄H₉) (OC₂H₅) ₂, (C₂H₅) ₃Csi (t-C₄H₉) (OC₂H₅) ₂, (C₂H₅) ₃CSi (n-C₅H₁₁) (OC₂H₅) ₂, (C₂H₅) ₃CSi (c-C₅H₉) (OC₂H₅) ₂, (C₂H₅) ₃CSi (n-C₆H₁₃) (OC₂H₅) ₂, (C₂H₅) ₃CSi (c-C₆H₁₁) (OC₂H₅) ₂, H (CH₃) ₂C (CH₃) ₂CSi (CH₃) (OC₂H₅) ₂, H (CH₃) ₂C (CH₃) ₂CSi (C₂H₅) (OC₂H₅) ₂, H (CH₃) ₂C (CH₃) ₂CSi (n-C₃H₇) (OC₂H₅) ₂, H (CH₃) ₂C (CH₃) ₂CSi (i-  C₃H₇) (OC₂H₅) ₂, H (CH₃) ₂C (CH₃) ₂CSi (n-C₄H₉) (OC₂H₅) ₂, H (CH₃) ₂C (CH₃) ₂C (CH₃) Si (O-n-C₃H₇) ₂, H (CH₃) ₂C (CH₃) ₂CSi (CH₃) (O-i- C₃H₇) ₂, H (CH₃) ₂C (CH₃) ₂CSi (CH₃) (O-i-C₃H₇) ₂, H (CH₃) ₂C (CH₃) ₂CSi (CH₃) (O-n-C₄H₉) ₂, H (CH₃) ₂C (CH₃) ₂CSi (C₂H₅) (O-n- C₃H₇) ₂, (CH₃) ₂ (C₂H₅) CSi (CH₃) (OC₂H₅) ₂, (CH₃) ₂ (C₂H₅) CSi (CH₃) (O-n- C₃H₇) ₂, (CH₃) ₂ (C₂H₅) CSi (CH₃) (O-n-C₄H₉) ₂, (CH₃) ₂ (C₂H₅) CSi (C₂H₅) (O- n-C₄H₉) ₂, (CH₃) ₃CSi (O₂H₅) ₃, (CH₃) ₃CSi (O-n-C₃H₇) ₃, (CH₃) ₃CSi (O-i- C₃H₇) ₃, (CH₃) ₃CSi (O-n-C₄H₉) ₃, (CH₃) ₃CSi (O-i-C₄H₉) ₃, (CH₃) ₃CSi (O- t-C₄H₉) ₃, (CH₃) ₃CSi (O-n-C₆H₁₂) ₃, (CH₃) ₃CSi (O-n-C₈H₁₇) ₃, (CH₃) ₃CSi (O-n-C₁₀H₂₁) ₃, (CH₃) ₂ (C₂H₅) CSi (OC₃H₅) ₃, (CH₃) ₂ (C₂H₅) CSi (O-n-C₃H₇) ₃, (CH₃) ₂ (C₂H₅) CSi (O-i-C₃H₇) ₃, (CH₃) ₂ (C₂H₅) CSi (O-n-C₄H₉) ₃, (CH₃) ₂ (C₂H₅) CSi (O-i-C₄H₉) ₃, (CH₃) ₂ (C₂H₅) CSi (O-t-C₄H₉) ₃, (CH₃) ₂ (C₂H₅) CSi (O-n-C₆H₁₂) ₃, (CH₃) ₂ (C₂H₅) CSi (O-n-C₈H₁₇) ₃, (CH₃) ₂ (C₂H₅) CSi (O-n-C₁₀H₂₁) ₃, (CH₃) (C₂H₅) ₂CSi (OC₂H₅) ₃, (CH₃) (C₂H₅) ₂CSi (O-n-C₃H₇) ₃, (CH₃) (C₂H₅) ₂CSi (O-i-C₃H₇) ₃, (CH₃) (C₂H₅) ₂CSi (O-n-C₄H₉) ₃, (CH₃) (C₂H₅) ₂CSi (O-i-C₄H₉) ₃, (CH₃) (C₂H₅) ₂CSi (O-t-C₄H₉) ₃, (CH₃) (C₂H₅) ₂CSi (O-n-C₆H₁₃) ₃, (CH₃) (C₂H₅) ₂CSi (O-n-C₈H₁₇) ₃, (CH₃) (C₂H₅) ₂CSi (O-n-C₁₀H₂₁) ₃, H (CH₃) ₂C (CH₃) ₂CSi (OC₂H₅) ₃, H (CH₃) ₂C (CH₃) ₂CSi (O-n-C₂H₇) ₃, H (CH₃) ₂C (CH₃) ₂CSi (O-i-C₃H₇) ₃, H (CH₃) ₂C (CH₃) ₂CSi (O-n-C₄H₉) ₃, H (CH₃) ₂C (CH₃) ₂CSi (O-i-C₄H₉) ₃, H (CH₃) ₂C (CH₃) ₂CSi (O-t-C₄H₉) ₃, H (CH₃) ₂C (CH₃) ₂CSi (O-n-C₆H₁₃) ₃, H (CH₃) ₂C (CH₃) C (CH₃) ₂CSi (O-n-C₈H₁₇) ₃, H (CH₃) ₂C (CH₃) ₂CSi (O-n- C₁₀H₂₁) ₃, (CH₃) ₃CSi (CH₃) (OC₂H₅) (O-n-C₃H₇), (CH₃) ₃CSi (CH₃) (OC₂H₅) (O-n-C₄H₉), (CH₃) ₃CSi (CH₃) (OC₂H₅) (O-n- C₈H₁₇),

As noted above, component (A) can present invention, if necessary, in addition to  above essential components optional Components included. The following connections are in suitably as such optional components used.

(A) vinyl silane compounds

Vinylsilane compounds for use in the present Invention can have a structure in which a Vinyl group (CH₂ = CH-) at least one hydrogen atom in Monosilane (SiH₄) replaced and in which a halogen (preferably Cl), an alkyl group (preferably one Hydrocarbon group having 1 to 12 carbon atoms), a Aryl group (preferably phenyl), an alkoxy group (preferably an alkoxy group with 1 to 12 Carbon atoms) or the like some of the remaining ones Hydrogen atoms replaced.

The vinyl silane compounds can specifically include the following include: CH₂ = CH-SiH₃, CH₂ = CH-SiH₂ (CH₃), CH₂ = CH-SiH (CH₃) ₂, CH₂ = CH-Si (CH₃) ₃, CH₂ = SiCl₃, CH₂ = CH-SiCl₂ (CH₃), CH₂ = CH-SiH (CH₃) ₂, CH₂ = CH-SiH (Cl) (CH₃), CH₂ = CH-Si (C₂H₅) ₃, CH₂ = CH-SiCl (C₂H₅) ₂, CH₂ = CH-SiCl₂ (C₂H₅), CH₂ = CH-Si (CH₃) ₂ (C₂H₅), CH₂ = CH-Si (CH₃) (C₂H₅) ₂, CH₂ = CH-Si (n-C₄H₉), CH₂ = CH-Si (C₆H₅) ₃, CH₂ = CH-Si (CH₃) (C₆H₅) ₂, CH₂ = CH-Si (CH₃) (C₆H₅), CH₂ = CH-Si (CH₃) ₂ (C₆H₄) CH₃), (CH₂ = CH) (CH₃) ₂Si-O-Si (CH₃) ₂ (CH = CH₂), (CH₂ = CH) ₂SiH₂, (CH₂ = CH) ₂SiCl₂, (CH₂ = CH) ₂Si (CH₃) ₂ and (CH₂ = CH) ₂Si (C₆H₅) ₂.

(B) Organometallic compounds

Organometallic compounds of metals, belonging to groups I to III of the periodic table, be used. The organometallic connections to the Have use in the present invention at least  an organic group-metal bond. Such organic Groups are typically hydrocarbon groups, in which the number of carbon atoms is generally 1 to 20, preferably 1 to 6. At least one valence of Metal of the organometallic compound is with one organic group satisfied as stated above and the remaining valence (valences) of the same (if there are some) with a hydrogen atom, a Halogen atom, a hydrocarbyloxy group (the number of Carbon atoms can generally be 1 to 20, preferably 1 to 6), or with another metal in the same organometallic compound via oxygen atom (e.g. -O- Al (CH₃) - in the case of methylalumoxane) or the like be satisfied.

Such organometallic compounds can in particular include the following: (a) Organolithium compounds, e.g. B. Methyl lithium, n-butyllithium and t-butyllithium; (b) Organomagnesium compounds, e.g. B. butylethyl magnesium, Dibutylmagnesium, Hexylethylmagnesium, Butylmagnesiumchlorid and t-butyl magnesium bromide; (c) organozinc compounds such as Diethyl zinc and dibutyl zinc; and (d) Organoaluminium compounds, such as. B. trimethyl aluminum, Triethyl aluminum, triisobutyl aluminum, tri-n- hexylaluminium, diethylaluminium chloride, Diethyl aluminum halide, diethyl aluminum ethoxide, Ethyl aluminum sesquichloride, ethyl aluminum dichloride and Methylalumoxane. Organoaluminum compounds are special prefers.

Each of the optional components (A) and (B) above can be used individually or as a mixture of two or more be used. The use of the optional components can enhance the effects of the present invention.  

Production of component (A)

Component (A) can be gradual or simultaneous contacting those described above essential and optional components and washing the resulting product with an organic Solvents, e.g. B. a hydrocarbon solvent or a halogenated hydrocarbon solvent, in an intermediate step or in a final step will.

Thus, component (A) can be carried out in a two-stage process are prepared, the solid component (A), the Titanium, magnesium and a halogen as essential components contains, is manufactured first, and with the solid product the silicon compound (A2) is brought into contact; or it can be made by a one-step process, wherein the silicon compound (A2) in the process of Production of the solid component (A1) may be present is left so as to directly produce the component (A). Of these methods, the first is the method mentioned prefers.

The conditions for making contact between the Components to form component (A) are not particularly limited as long as the intended effects of present invention can be achieved. In general however, the following conditions are applied. The Contact temperature is preferably in the range of about between -50 to about 200 ° C, preferably between 0 and 100 ° C. The contact can be made using mechanical means, such as B. a rotary ball mill, a vibration mill, a jet mill or a stirring mill, or by a method which involves diluting the  Components with an inert diluent and stirring of the system. The inert diluent can be a aliphatic or aromatic hydrocarbon or a Halogenated hydrocarbon or a polysiloxane.

Although the amounts of the respective components to form component (A) is not particularly limited, as long as the intended effects of the present Invention can be achieved in the following amounts general applied. The molar ratio of Titanium compound to the magnesium compound can range between 0.0001 to 1000, preferably between 0.01 and 10, lie. If a halogen compound as a halogen source can be used, the molar ratio of the halogen compound to the magnesium compound in the range between 0.01 and 1000, preferably between 0.1 and 100, are regardless of whether the titanium compound and / or the Magnesium compound contains a halogen or Not. The silicon compound, component (A2), can be in such an amount that the molar ratio from silicon to titanium in the resulting component (A) in the range between 0.01 to 1000, preferably 0.1 and 100, will be.

If the vinylsilane compound is used, it can be used in such an amount that the Molar ratio of vinylsilane compound to the titanium component in the resulting component (A) in the range between 0.001 to 1000, preferably between 0.01 and 100. If the aluminum and boron compounds can be used the molar ratios of these compounds to the Magnesium compound in the range between 0.001 and 100, preferably between 0.01 and 1. If the Electron donor can be used, the molar ratio  Electron donor to the magnesium compound in the area between 0.001 and 10, preferably between 0.01 and 5, lie.

Component (A) can be prepared by the Components (A1) and (A2) using if necessary other components such. B. an electron donor to Example using one of the following methods To be contacted:

• (a) a method in which a magnesium halide with a Electron donor, a titanium-containing compound, a silicon compound and a sulfonate in contact brought;
• (b) a process in which alumina or magnesium oxide is treated with a phosphorus halide compound, and the treated alumina or magnesia a magnesium halide, an electron donor, one Silicon compound, a titanium halide compound and is contacted with a sulfonate;
• (c) a process in which a magnesium halide is contacted with titanium tetraalkoxide and a specific polymeric silicon compound, the resulting solid component is contacted with a titanium halide and / or a silicon halide, the resulting reaction product is contacted with an inert organic solvent and then contacting the reaction product with a silicon compound and a sulfonate compound, either simultaneously or stepwise. Preferred polymeric silicon compounds are those which are represented by the formula - (- SiH (R⁸) -O-) _r - (in which R⁸ is a hydrocarbon group having 1 to 10 carbon atoms, r denotes a degree of polymerization such that the viscosity of the polymeric silicon compound ranges from 1 to 100 centistokes, and specific preferred examples of the polymeric silicon compound include methylhydropolysiloxane, ethylhydropolysiloxane, phenylhydropolysiloxane, cyclohexylhydropolysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7,9-pentamethylcyclopentasiloxane;
• (d) a method in which a magnesium compound in Titanium tetraalkoxide and / or an electron donor is resolved, a fixed component with a Halogenating agent or one Titanium halide compound is deposited, and the fixed component then either simultaneously or gradually with a silicon compound, one Titanium compound and a sulfonate compound in contact brought;
• (e) a method in which an organomagnesium compound, e.g. B. a Grignard reagent with a Halogenating agent, a reducing agent or the like is brought into contact, the resultant Product with an electron donor, if necessary, in Is brought in contact, and the resultant Product either at the same time or step by step a silicon compound, a titanium compound and is contacted with a sulfonate compound; and  
• (f) a method in which an alkoxymagnesium compound either simultaneously or step by step with one Halogenating agent and / or a titanium compound, a silicon compound and a sulfonate compound in the presence or absence of an electron donor in Is brought in contact or by this separately be brought into contact with each other.

Among the methods listed above, methods (a), (c), (d) and (f) preferred. Component (A) can with an inert organic solvent, e.g. B. one aliphatic or aromatic Hydrocarbon solvents (e.g. hexane, heptane, toluene or cyclohexane) or a halogenated Hydrocarbon solvents (e.g. n-butyl chloride, 1,2- Dichloroethane, carbon tetrachloride or chlorobenzene) in an intermediate step or a final step its manufacture.

Component (A) for use in the present Invention can also be one that Prepolymerization process which involves polymerizing a a compound containing vinyl group, e.g. B. an olefin, a diene compound or styrene, in the presence of the above made component (A). The olefins, to be used for the prepolymerization have 2 to 20 carbon atoms and examples are: ethylene, Propylene, 1-butene, 3-methylbutene-1,1-pentene, 1-hexene, 4- Methylpentene-1,1-octene, 1-decene, 1-undecene and 1-eicosen. Specific examples of the diene compounds can be 1,3- Butadiene, isoprene, 1,4-hexadiene, 1,5-hexadiene, 1,3- Pentadiene, 1,4-pentadiene, 2,4-pentadiene, 2,6-octadiene, cis- 2, trans-4-hexadiene, trans-2, trans-4-hexadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,4-heptadiene,  Dicyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, Cyclopentadiene, 1,3-cycloheptadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,9-decadiene, 1,13-tetradecadiene, p-divinylbenzene, m-divinylbenzene, o-divinylbenzene and Include dicyclopentadiene. The styrenes can be styrene, α-methylstyrene, allylbenzene and chlorostyrene include.

The reaction conditions in the above Prepolymerization processes are not special limited as long as the intended effects of present invention can be achieved; however can the following conditions are generally applied. The amount of prepolymerized, a vinyl group containing compound can range between 0.01 to 100 g, preferably between 0.1 to 50 g, more preferred between 0.5 and 10 g, per 1 g of the solid Catalyst component. The reaction temperature can in the prepolymerization in the range between -150 to 150 ° C, preferably between 0 and 100 ° C. The Reaction temperature of the prepolymerization is preferred lower than that of the "main polymerization" of propylene. in the generally the reaction is preferably carried out with stirring executed. In this case, an inert solvent, e.g. B. n-hexane or n-heptane can be used.

(2) Organoaluminum compound component

The organoaluminum compound (component (B)) which can be used in the present invention may be one represented by the general formula R⁹ _3-s AlX _s or R¹⁰ _3-t Al (OR¹¹) _t (in which R⁹ and R¹⁰ each have one Represent a hydrocarbon group having 1 to 20 carbon atoms or hydrogen, R 11 is a hydrocarbon group, X is a halogen, and s and t 0 s <3, 0 <t <3). Specific examples include (a) trialkyl aluminum, e.g. B. trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum and tridecyl aluminum; (b) alkyl aluminum halides, e.g. B. diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride and ethyl aluminum dichloride; (c) alkyl aluminum hydrides, e.g. B. diethyl aluminum hydride and diisobutyl aluminum hydride; and (d) alkyl aluminum alkoxides, e.g. B. diethyl aluminum ethoxide and diethyl aluminum phenoxide.

These organoaluminum compounds (a) to (d) can be used in Combination can be used. For example, the Combination of triethyl aluminum and Diethyl aluminum ethoxide, the combination of Diethyl aluminum monochloride and diethyl aluminum ethoxide, the Combination of ethyl aluminum dichloride and Ethyl aluminum diethoxide, the combination of Triethyl aluminum, diethyl aluminum ethoxide and Diethyl aluminum monochloride, etc. can be used.

In addition, the organic aluminum compounds (a) to (d) with alumoxanes, e.g. B. methylalumoxane, ethylalumoxane and isobutylalumoxane can be combined.

(3) Silicon compound component

The silicon compound (component (C)) to be used in the present invention is represented by the general formula R⁴ _4-n Si (OR⁵) _n (in which R⁴ is a hydrocarbon group, R⁵ is a hydrocarbon group having 2 or more carbon atoms, and 1 n 4). The number of carbon atoms in R⁴ is generally in the range from 1 to 30, preferably from 1 to 20; and the number of carbon atoms in R⁵ is generally in the range of 2 to 20, preferably 2 to 10.

Specific examples of such silicon compounds include:
Si (OC₂H₅) ₄, Si (On-C₃H₇) ₄, Si (Oi-C₃H₇) ₄, Si (On-C₄H₉) ₄, Si (O- i-C₄H₉) ₄, Si (Os-C₄H₉) ₄, Si ( Ot-C₄H₉) ₄, Si (On-C₆H₁₃) ₄, CH₃Si (OC₂H₅) ₃, C₂H₅Si (OC₂H₅) ₃, CH₂ = CH-Si (OC₂H₅) ₃, n- C₃H₇Si (OC₂H₅) ₃, i-C₃H₇Si (O ₃ n-C₄H₉Si (OC₂H₅) ₃, n- C₅H₁₇Si (OC₂H₅) ₃, C₆H₅Si (OC₂H₅) ₃, (CH₃) ₂Si (OC₂H₅) ₂, (C₂H₅) ₂Si (OC₂H₅) O₂, (CH₂ = ₂, (n-C₃H₇) ₂Si (OC₂H₅) ₂, (i- C₃H₇) ₂Si (OC₂H₅) ₂, (C₆H₅) ₂Si (OC₂H₅) ₂, (CH₃) ₂Si (On-C₃H₇) ₂, (CH₃) ₂Si (Oi -C₃H₇) ₂, (CH₃) ₂Si (On-C₄H₉) ₂, (CH₃) ₂Si (Oi-C₄H₉) ₂, (CH₃) ₂Si (Os-C₄H₉) ₂, (CH₃) ₂Si (Ot-C₄H₉) ₂, ( CH₃) ₃Si (OC₂H₅), (CH₃) ₃Si (On-C₃H₇), (CH₃) ₃Si (Oi-C₃H₇), (CH₃) ₃Si (On-C₄H₉), (C₃) ₃Si (Oi-C₄H₉), (CH₃) ₃Si (Os-C₄H₉), (CH₃) ₃Si (Ot-C₄H₉), (C₂H₅) ₃Si (OC₂H₅), (n-C₃H₅) ₃Si (OC₂H₅), (iC H₅) ₃Si (OC₂H₅), (C₅H₅) ₃Si (OC₂H₅), (CH₃) ₃CSi (CH₃) (OC₂H₅) ₂, (CH₃) ₃CSi (CH₃) (On- C₃H₇) ₂, (CH₃) ₃CSi (CH₃) (Oi -C₃H₇) ₂, (CH₃) ₃CSi (CH₃) (On-C₄H₉) ₂, (CH₃) ₃CSi (CH₃) (Oi-C₄H₉) ₂, (CH₃) ₃CSi (CH₃) (Ot-C₄H₉) ₂, (CH₃) ₂CSi (CH₃) (On-C₆H₁₃) ₂, (CH₃) ₃CSi (CH₃) (On-C₈H₁₇) ₂, (CH₃) ₃CSi (CH₃) (On-C₁₀H₂) ₂, (CH₃) ₃CSi (C₂H₅) (OC₂H₅) ₂ , (CH₃) ₃CSi (n-C₃H₇) (OC₂H₅) ₂, (CH₃) ₃CSi (i-C₃H₇) (OC₂H₅) ₂, (CH₃) ₃CSi (n-C₄H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (i- C₄H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (s-C₄H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (t-C₄H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (n-C₅H₁₁) (OC₂H₅) ₂, ( CH₃) ₃CSi (c-C₅H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (n-C₆H₁₃) (OC₂H₅) ₂, (CH₃) ₃CSi (c-C₆H₁₁) (OC₂H₅) ₂, (CH₃) ₃CSi (C₂H₅) (On -C₃H₇) ₂, (CH₃) ₃CSi (C₂H₅) (Oi-C₃H₇) ₂, (CH₃) ₃CSi (C₂H₅) (On-C₄H₉) ₂, (CH₃) ₃CSi (C H₅) (Oi-C₄H₉) ₂, (CH₃) ₃CSi (C₂H₅) (Os-C₄H₉) ₂, (CH₃) ₃CSi (C₂H₅) (Ot-C₄H₉) ₄) ₂, (CH₃) ₃CSiC (C₂H₅) (On-C₆H₁₃ ) ₂, (CH₃) ₃CSi (C₂H₅) (On-C₈H₁₇) ₂, (CH₃) ₃CSi (C₂H₅) (On-C₁₀H₂₁) ₂, (CH₃) ₃CSi (i-C₃H₇) (On-C₃H₇) ₂, (CH₃) ₃CSi (i-C₃H₇) (Oi-C₃H₇) ₂, (CH₃) ₃CSi (i-C₃H₇) (On-C₄H₉) ₂, (CH₃) ₃CSi (i-C₃H₇) (Oi-C₄H₉) ₂, (CH₃) ₃CSi ( i-C₃H₇) (Os-C₄H₉) ₂, (CH₃) ₃CSi (i-C₃H₇) (Ot-C₄H₉) ₂, (CH₃) ₃CSi (i-C₃H₇) (On-C₆H₁₃) ₂, (CH₃) ₃CSi (i- C₃H₇) (On-C₈H₁₇) ₂, (CH₃) ₃CSi (i-C₃H₇) (On-C₁₀H₂₁) ₂, (CH₃) ₃CSi (On-C₃H₇) (OC₂H₅) ₂, (CH₂) ₃CSi (Oi-C₃H₇) (OC₂H₅ ), (CH₃) ₃CSi (On-C₄H₉) (OC₂H₅) ₂, (CH₃) ₃CSi (Oi-C₄H₉) (OC₂H₅), (CH₃) ₃CSi (Os-C₄H₉) (OC₂H₅), (CH₃) ₃CSi (Ot-C₄H₉ ) (OC₂H₅) ₂, (CH₃) ₂₃CSi (On-C₅H₁₁) (OC₂H₅) ₂, (CH₃) ₃CSi (Oc-C₅H₉) (OC₂H₅) ₂, (C₃) ₃CSi (On-C₆H ₁₃) ₂, (CH₃) ₃CSi (Oc-C₆H₁₁) (OC₂H₅) ₂, (i- C₃H₇) ₂Si (OC₂H₅) ₂, (i-C₄H₉) ₂Si (OC₂H₅) ₂, (s-C₄H₉) ₂Si (OC₂H₅) , (neo- C₅H₁₁) ₂Si (OC₂H₅) ₂, (c-C₅H₉) ₂Si (OC₂H₅) ₂, (c-C₅H₉) ₂Si (On-C₃H₇) ₂, (c-C₅H₉) ₂Si (On-C₄H₉) ₂, ( c-C₅H₉) ₂Si (On-C₅H₁₁) ₂, (c-C₅H₉) ₂Si (On-C₈H₁₇) ₂, (c-C₆H₁₁) ₂Si (OC₂H₅) ₂, (c-C₆H₁₁) ₂Si (On-C₃H₇) ₂, ( c- C₈H₁₁) ₂Si (On-C₄H₉) ₂, (c-C₅H₁₁) ₂Si (On-C₅H₁₁) ₂, (c-C₆H₁₁) ₂Si (On- C₈H₁₇) ₂, (c-C₆H₁₁) Si (CH₃) (OC₂H₅) ₂, (c-C₆H₁₁) Si (CH₃) (On-C₃H₇) ₂, (-cC₆H₁₁) Si (CH₃) (On-C₄H₉) ₂, (c-C₆H₁₁) Si (CH₃) (On-C₅H₁₁) ₂, ( c- C₆H₁₁) Si (CH₃) (On-C₈H₁₇) ₂, (c-C₆H₁₁) Si (C₂H₅) (OC₂H₅) ₂, (c- C₆H₁₁) Si (n-C₄H₉) (OC₂H₅) ₂, (c-C₆H₁₁) Si (c-C₅H₉) (OC₂H₅) ₂, (C₂H₅) ₃CSi (CH₃) (OC₂H₅) (OC₂H₅) ₂, (C₂H₅) ₃CSi (CH₃) (On-C H₇) ₂, (C₂H₅) ₃CSi (CH₃) (Oi-C₃H₇) ₂, (C₂H₅) ₃CSi (CH₃) (On-C₄H₉) ₂, (C₂H₅) ₃CSi (CH₃) (Oi-C₄H₉) ₂, (C₂H₅) ₃CSi (CH₃) (Ot-C₄H₉) ₂, (C₂H₅) ₃CSi (CH₃) (On-C₆H₁₃) ₂, (C₂H₅) ₃CSi (CH₃) (On-C₈H₁₇) ₂, (C₂H₅) ₃CSi (CH₃) (On-C₁₀H₂₁) ₂, (C₂H₅) CSi (C₂H₅) (OC₂H₅) ₂, (C₂H₅) ₃CSi (n-C₃H₇) (OC₂H₅) ₂, (C₂H₅) ₃CSi (i-C₃H₇) (OC₂H₅) ₂, (C₂H₅) ₃CSi (n- ) (OC₂H₅) ₂, (C₂H₅) ₃CSi (i-C₄H₉) (OC₂H₅) ₂, (C₂H₅) ₃CSi (S-C₄H₉) (OC₂H₅) ₂, (C₂H₅) ₃CSi (t-C₄H₉) (OC₂H₅H) ₂, (C ) ₃CSi (n-C₅H₁₁) (OC₂H₅) ₂, (C₂H₅) ₃CSi (c-C₅H₉) (OC₂H₅) ₂, (C₂H₅) ₃CSi (n-C₆H₁₃) (OC₂H₅) ₂, (C₂H₅) ₃CSi (c-C₆H₆) OC₂H₅) ₂, H (CH₃) ₂C (CH₃) ₂CSi (CH₃) (OC₂H₅) ₂, H (CH₃) ₂C (CH₃) ₂CSi (C₂H₅) (OC₂H₅) ₂, H (CH₃) ₂C (CH₃) ₂CSi (n- C₃H₇) (OC₂H₅) ₂, H (CH₃) ₂C (CH₃) ₂CSi (i- C₃H₇) (OC₂H₅) ₂, H (CH₃) ₂C (CH₃) ₂CSi (n-C₄H₉) (OC₂H₅) ₂, H (CH₃) ₂C (CH₃) ₂C (CH₃) Si (On-C₃H₇) ₂, H (CH₃) ₂C (CH₃) ₂CSi (CH₃) (Oi- C₃H₇) ₂, H (CH₃) ₂C (CH₃) ₂CSi (CH₃) (On-C₄H₉) ₂, H (CH₃) ₂C (CH₃) ₂CSi (C₂H₅) (On-C₃H₇) ₂, (CH₃ ) ₂ (C₂H₅) CSi (CH₃) (OC₂H₅) ₂, (CH₃) ₂ (C₂H₅) CSi (CH₃) (On-C₃H₇) ₂, (CH₃) ₂ (C₂H₅) CSi (CH₃) (On-C₄H₉) ₂, (CH₃) ₂ (C₂H₅) CSi (C₂H₅) (On-C₄H₉) ₂, (CH₃) ₃CSi (OC₂H₅) ₃, (CH₃) ₃CSi (O- n-C₃H₇) ₃, (CH₃) ₃CSi (Oi-C₃H₇) ₃ , (CH₃) ₃CSi (On-C₄H₉) ₃, (CH₃) ₃CSi (Oi-C₄H₉) ₃, (CH₃) ₃CSi (Ot-C₄H₉) ₃, (CH₃) ₃CSi (On- C₆H₁₂) ₃, (CH₃) ₃CSi ( On-C₈H₁₇) ₃, (CH₃) ₃CSi (On-C₁₀H₂₁) ₃, (CH₃) ₂ (C₂H₅) CSi (OC₂H₅) ₃, (CH₃) ₂ (C₂H₅) CSi (On-C₃H₇) ₃, (CH₃) ₂ ( C₂H₅) CSi (Oi-C₃H₇) ₃, (CH₃) ₂ (C₂H₅) CSi (On-C₄H₉) ₃, (CH₃) ₂ (C₂H₅) CSi (Oi-C₄H₉) ₃, (CH₃) ₂ (C₂H₅) CSi (Ot -C₄H₉) ₃, (CH₃) ₂ (C₂H₅) CSi (Oi-C₆H₁₃) ₃, (CH₃) ₂ (C₂H₅) CSi (On-C₅H₁₇), (CH₃) ₂ (C₂H₅) CSi (On-C₁₀H₂₁) ₃, (CH₃) (C₂H₅) ₂CSi (OC₂H₅) ₃, (CH₃) (C₂H₅) ₂CSi (On-C₃H₇) ₃, (CH₃) (C₂H₅) ₂CSi (Oi-C₃H₇) ₃, (CH₃) (C₂H₅) ₂CSi (On-C₄H₉) ₃, (CH₃) (C₂H₅) ₂CSi (Oi-C₄H₉) ₃, (CH₃) (C₂H₅) ₂CSi (Ot-C₄H₉) ₃, (CH₃) (C₂H₅) ₂CS1 (On-C₆H₁₃) ₃, (CH₃) (C₂H₅) ₂CSi (On-C₈H₁₇) ₃, (CH₃) (C₂H₅) ₂CSi (On-C₁₀H₂₁) ₃, H (CH₃) ₂C (CH₃) ₂CSi (OC₂H₅) ₃, H (CH₃) ₂C (CH₃) ₂CSi (On-C₃H₇) ₃, H (CH₃) ₂C ( CH₃) ₂CSi (Oi-C₃H₇) ₃, H (CH₃) ₂C (CH₃) ₂CSi (On-C₄H₉) ₃, H (CH₃) ₂C (CH₃) ₂CSi (Oi-C₄H₉) ₃, H (CH₃) ₂C (CH₃) ₂CSi (Ot-C₄H₉) ₃, H (CH₃) ₂C (CH₃) ₂CSi (On-C₆H₁₃) ₃, H (CH₃) ₂C (CH₃) ₂CSi (On-C₈H₁₇) ₃, H (CH₃) ₂C (CH₃) ₂CSi ( On-C₁₀H₂₁) ₃, (CH₃) ₃CSi (CH₃) (OC₂H₅) (On-C₃H₇), (CH₃) ₃CSi (CH₃) (OC₂H₅) (On-C₄H₉), (CH₃) ₃ Si (CH₃) (OC₂H₅) (On- C₅H₁₇),

In the polymerization of propylene according to the present Invention are the amounts of components (A), (B) and (C), to be used, not particularly limited, as long as the beneficial effects of the present invention be achieved. However, the following quantities can be found in general use. The molar ratio of Component (B) to the titanium compound of component (A) can range between 0.001 and 10,000, preferably between 1 and 1000. The molar ratio of Component (C) to component (B) can range between 0.001 and 1000, preferably between 0.01 and 10, more preferably between 0.05 and 2.  

Polymerization of propylene

The polymerization of propylene to produce the Low crystallinity polypropylene according to the present invention can be carried out using any Polymerization techniques are carried out, for example as a slurry polymerization using a Hydrocarbon solvent, as solvent-free Liquid phase polymerization (bulk polymerization), Solution and vapor phase polymerization. In the case of slurry polymerization aliphatic or aromatic solvents, e.g. B. pentane, Hexane, heptane, cyclohexane, benzene and toluene or mixtures of the above, can be used as a solvent. About that In addition, the polymerization can be continuous Polymerization, batch polymerization, one Multi-stage polymerization or a polymerization that the Includes prepolymerization step. The Polymerization temperature can generally range between 20 and 200 ° C, preferably between 50 and 150 ° C, lie. The polymerization pressure can range between Atmospheric pressure and about 300 kg / cm², preferably between Atmospheric pressure and 100 kg / cm². As is known, can Hydrogen in polymerisation as a molecular weight Modifiers are used.

The following examples illustrate the present invention closer, but should not limit them to these.

The following procedures and equipment were used for measurement the physical properties of the polypropylenes described in the examples obtained were used.  

MFR

Apparatus: Melt flow index measuring apparatus manufactured by Takara Co., Ltd.
Measurement method according to JIS-K6758

CXS

Measuring method: a sample (about 5 g) was measured precisely and completely dissolved in xylene (300 ml) at 140 ° C, then the solution was cooled to 23 ° C and 12 hours ditched. Filtration was then carried out and the amount of solids dissolved in the filtrate became isolated. The weight ratio of the isolated solid the sample was determined.

Differential scanning calorimeter (DSC)

Apparatus: DSC-2 manufactured by PERKIN-ELMER Co., Ltd.
Measurement method: a sample (about 5 mg) was melted at 200 ° C in 3 minutes, then the temperature was reduced to 30 ° C at a rate of 10 g / min. The temperature was then increased to 200 ° C. at a rate of 10 g / min. A melting curve was obtained in this way; an endothermic main peak temperature (Tmp) was determined from the curve.

Cross Fractionation Chromatograph (CFC)

Apparatus: D150A Cross Fractionation Chromatograph manufactured by Mitsubishi Chemical Co., Ltd.
Measuring method: a sample of polymer solution (solvent: o-dichlorobenzene) was fed to a temperature increase elution fractionation (TREF), the temperature of the solution being raised from 0 ° C. to 140 ° C. in 24 hours. An elution curve was obtained in this way and the weight ratio of the polymer fraction eluted at a temperature below 80 ° C. to the total polymer was determined from this.

13 C NMR

Apparatus: GSX-270 manufactured by JEOL LTD.
Measuring method: the proton decoupling method was carried out at a measuring temperature of 130 ° C. using o-dichlorobenzene / heavy benzene as solvent, the weight ratio of the mmmm component to the total polymer being determined.

example 1 Production of component (A)

200 ml of dehydrated and deoxidized n-heptane were in a flask filled with sufficient nitrogen, then 0.4 mol of MgCl₂ and 0.8 mol of Ti (O-n-C₄H₉) Carried out the reaction filled at 95 ° C for 2 hours. After the reaction, the temperature of the Systems reduced to 40 ° C. Then 48 ml Methyl hydropolysiloxane (20 centistoke) in the flask given to conduct a reaction over 3 hours. The resulting solid component was washed with n-heptane.

Next, 50 ml of n-heptane that was in the same Way as had been cleaned up in one in Sufficiently flushed flask with nitrogen were introduced, then 0.24 mol, based on Mg atom, of above synthesized solid component in the flask  given. Then 0.4 mol of SiCl₄ with 25 ml of n-heptane mixed; the mixture was stirred over a period of 30 Minutes into the flask at 30 ° C, and the mixture was reacted at 70 ° C for 3 hours. After this the reaction was complete, the reaction product was Washed heptane. Thereafter, 1.6 ml (CH₃) ₃CSi (CH₃) (OC₂H₅) ₂ added as a silicon compound in the flask, so that Reaction product was brought into contact with it. After this the contact had been made, the resulting Product sufficiently washed with n-heptane, one Component (A) was obtained, the magnesium chloride as Main component included. The titanium content in the component (A) was 2.3% by weight.

Polymerization of polypropylene

500 ml of sufficiently dehydrated and deoxidized n- Heptane, 125 ml triethyl aluminum as component (B), 20.8 mg (CH₃) ₃CSi (CH₃) (OC₂H₅) ₂ as component (C) and 15 mg of the above Component (A) produced were placed in a stainless steel Steel autoclaves with an internal volume of 1.5 liters, the was equipped with a stirrer and a thermostat, given. Then 60 ml of hydrogen were in the autoclave initiated, and there were temperature and pressure of the system to carry out the polymerization of propylene under the following conditions increased: polymerization pressure = 5 kg / cm² G, polymerization temperature = 75 ° C and polymerization time = 2 hours. After the polymerization, the resulting polymer slurry of a filtration subjected to separate the polymer. After that it was Polymer dried. As a result, 289.5 g of polymer receive. 0.48 g of polymer was obtained from the filtrate. The polymer obtained had an MFR of 4.5 g / 10 min, a Xylene solubility (CXS) at 23 ° C of 2.8 wt .-%, a  Peak temperature (Tmp) of 160.1 ° C on a melting curve, obtained by DSC at a temperature below 80 ° C an eluted amount of 0.52 wt .-%, measured by CFC, and an isotactic Pentad fraction (mmmm) of 96.0%, measured by NMR.

Example 2 Production of component (A)

100 ml of dehydrated and deoxidized toluene were in a sufficiently flushed flask with nitrogen were given, then 20 g of Mg (OEt) ₂ to produce a Suspension introduced into the flask. Then 60 ml TiCl₄ placed in the flask and the temperature of the system increased from room temperature to 90 ° C. Then 3.3 ml Cellosolve acetate introduced into the flask and the temperature raised to 100 ° C, then a 3 hour reaction perform. After the reaction ended, that became Reaction product washed sufficiently with toluene. After that were 100 ml of TiCl₄ and 100 ml of toluene in the flask initiated a 3 hour reaction at 110 ° C perform. After the reaction ended, that became Reaction product sufficiently washed with n-heptane.

Next, 50 ml of n-heptane that was in the same Way as had been cleaned up in one in adequately given flasks purged with nitrogen; then 5 g of the above synthesized solid Component, 0.5 ml divinyldimethylsilane, 1.1 ml (i- C₃H₇) ₂Si (OC₂H₅) ₂ and 3.6 g Al (n-C₆H₁₃) ₃ added to the flask, where they are in contact with each other at 50 ° C for 2 hours brought. After that, the resulting product was in sufficiently with n-heptane to produce a  Component (A) washed. The titanium content of component (A) was 2.9% by weight.

Polymerization of propylene

The polymerization of propylene was carried out in the same way as in Example 1, except that the Polymerization temperature was changed to 85 ° C, and that 27.0 ml (CH₃) ₃CSi (CH₃) (O-n-C₄H₉) ₂ used as component (C) were. The result was that 301.7 g of polymer was obtained were. 0.66 g of polymer was obtained from the filtrate. The Polymer had an MFR of 6.2 g / 10 min, a xylene Solubility (CXS) at 23 ° C of 3.7 wt .-%, a Peak temperature (Tmp) of 157 ° C on a melting curve, which had been obtained by DSC, one at a temperature amount eluted below 80 ° C of 0.67% by weight by CFC, and an isotactic pentad fraction (mmmm) of 96.0% as measured by NMR.

Examples 3 to 5

Using the solid catalyst component (Component (A)) of Example 1 became the same Polymerization carried out as in Example 1, except that Silicon compounds, as shown in Table 1, when component (C) was used. The results are listed in Table 1.

Comparative Example 1

It became a solid catalyst component in the same Way as in Example 1, except that (CH₃) ₃CSi (CH₃) (OC₂H₅) ₂ as Component (A2) was not used. The Polymerization was carried out in the same manner as in Example 1  carried out. The result was that 168.6 g of polymer was obtained were. 1.10 g of polymer were obtained from the filtrate. The polymer obtained had an MFR of 7.8 g / 10 min, a Xylene solubility (CXS) at 23 ° C of 6.7 wt .-%, at a Melting curve obtained by DSC, a Peak temperature (Tmp) of 152.5 ° C, at one temperature of less than 180 ° C an eluted amount of 3.5 wt .-%, measured by CFC, and an isotactic pentad fraction (mmmm) of 92.0% as measured by NMR.

Comparative Example 2

Using the solid catalyst component (Component (A)) of Example 1 became the same Polymerization carried out as in Example, except that the Component (C) (CH₃) ₃CSi (CH₃) (OC₂H₅) ₂ was not used. The result was that 234.6 g of polymer was obtained. Out 1.20 g of polymer were obtained from the filtrate. The received Polymer had an MFR of 6.6 g / 10 min, a xylene Solubility (CXS) at 23 ° C of 5.5 wt .-%, at a Melting curve obtained by DSC, a Peak temperature (Tmp) of 154.8 ° C, at one temperature an eluted amount of 3.50% by weight below 180 ° C., measured by CFC, and an isotactic pentad fraction (mmmm) of 93.0% as measured by NMR.

Comparative Example 3

150 ml of dehydrated and deoxidized n-heptane were in given a flask sufficiently flushed with nitrogen, then 60 ml of TiCl₄ were passed into the flask. On the other hand, 120 ml of n-heptane and 9.5 g Diethyl aluminum chloride filled in a dropping funnel. Of the Flask was cooled to -10 ° C; and diethyl aluminum chloride  was added dropwise over a period of 3 hours Dropping funnel added to the contents of the flask. The The reaction was continued for another hour at -10 ° C drained. The temperature of the system was then over Increased to 65 ° C for 1 hour and the reaction for another Hour expired. After the reaction ended, the reaction product was sufficiently treated with n- Heptane washed using a solid titanium trichloride Composition was obtained.

Next, a mixed solution of 250 ml of n-heptane and 100 ml of diisoamyl ether to that obtained above Titanium trichloride composition given a 1 hour Carry out reaction at 35 ° C. After the reaction had ended, the reaction product became sufficient Way washed with n-heptane. After that, a mixed one Solution from 250 ml of n-heptane and 120 ml of TiCl₄ for 2 hours 65 ° C brought into contact with the above reaction product. After the reaction was over, the reaction product became adequately with n-heptane to obtain a solid catalyst component washed.

Polymerization of propylene

500 ml of sufficiently dehydrated and deoxidized n- Heptane, 500 mg of diethyl aluminum chloride and 50 mg of the above Solid catalyst component produced were in a Stainless steel autoclaves with an internal volume of 1.5 Liter with a stirrer and a thermostat was given. Then 350 ml of hydrogen were in the autoclave and the temperature and pressure of the Systems were used to carry out the polymerization of Propylene increased under the following conditions: Polymerization pressure = 5 kg / cm² G, polymerization temperature  = 65 ° C and polymerization time = 2 hours. after the Polymerization was complete, the resulting polymer Slurry to separate the polymer from a filtration subjected; the polymer was then dried. The As a result, 79.7 g of polymer was obtained. From the Filtrate gave 2.8 g of polymer. The polymer obtained had an MFR of 8.1 g / 10 min, xylene solubility (CXS) at 23 ° C of 3.4 wt .-%, at one by DSC obtained melting curve a peak temperature (Tmp) of 159.8 ° C, one eluted at a temperature below 80 ° C Amount of 5.1% by weight, measured by CFC and a Pentad isotactic fraction (mmmm) of 91.5%, measured by NMR.

The results of the above examples and comparative examples are listed in Table 1.  

Table 1

Claims (2)

1. Polypropylene resin that has the following physical properties:

• (1) a fluidity (MFR) of 0.1 to 1000 g / 10 min measured at 230 ° C under a load of 2.16 kg;
• (2) a xylene solubility (CXS) of 0.5 to 5.0% by weight at 23 ° C;
• (3) a main endothermic peak temperature (Tmp) of 153-163 ° C as determined on a melting curve measured with a differential scanning calorimeter (DSC);
• (4) at a temperature below 80 ° C, an eluted amount of 0.01 to 3.0% by weight as measured by a Cross Fractionation Chromatograph (CFC); and
• (5) an isotactic pentad fraction (mmmm) of 92.0 to 98.0% by weight as measured by 13 C-NMR.

2. A process for producing a polypropylene resin according to claim 1, which comprises the step of polymerizing propylene in the presence of a catalyst containing the combination of the following components (A), (B) and (C):
Component (A): a solid catalyst component obtained by contacting a component (A1) which is a solid component containing titanium, magnesium and a halogen as essential components with a component (A2) which is a component made of a silicon compound represented by the general formula R¹R² _3-m Si (OR³) _m (in which R¹ is a branched chain aliphatic hydrocarbon group or is a cyclic aliphatic hydrocarbon group; R² is a hydrocarbon group that is the same as or different from R¹ or one containing a hetero atom Is hydrocarbon group; R³ is a hydrocarbon group having two or more carbon atoms and is represented by 1 m 3);
Component (B): an organoaluminum compound component;
Component (C): a component made of a silicon compound represented by the general formula R⁴ _4-n Si (OR⁵) _n (in which R⁴ is a hydrocarbon group, R⁵ is a hydrocarbon group having 2 or more carbon atoms, and 1 n 4) .