JPH06298832A - Polymerization catalyst and preparation of high-impact polypropylene - Google Patents

Abstract

PURPOSE: To obtain an impact-resistant polypropylene having totally balanced properties while retaining high impact strength by polymerizing propylene in the presence of a fourth generation catalyst system in a reactor provided with a gas-phase fluidized bed.

CONSTITUTION: A catalyst system is prepared which contains a solid catalyst component (A) containing an internal strong electron donor obtained by reacting an Mg compound of formula I (wherein Q is an alkoxide, an aryloxide or the like; X is a halogen; and n is 0 or 1) with titanium tetrachloride in the presence of an organic acid chloride, a silicone compound (B) of formula II (wherein R and R' are each an alkyl or the like; and m is 0 or 1-3), an organoaluminum compound (C) of formula III (wherein R" is an alkyl; X is H or a halogen; and n is 1-3) and an external strong electron donor (D) selected from among ethers, esters, ketones, phenols, amines, amides, imines, etc. Propylene is polymerized in a gas phase in the presence of this catalyst system to produce the impact-resistant polypropylene.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a propylene polymerization catalyst containing magnesium tetrachloride supported titanium tetrachloride. The present invention also relates to a process for making impact polypropylene using a polymerization catalyst under gas phase fluidized bed reaction conditions. Further, the present invention relates to an improved impact polypropylene having improved balance properties as a whole when subjected to impact strength.

[0002]

A wide variety of propylene, homopolymers and copolymers (both crystalline and amorphous) are available.
It is produced in large quantities by the gas phase or slurry phase method.
In both of these methods, the use of high activity catalyst systems results in polypropylene resins with low levels of catalyst residues and low levels of amorphous polymer moieties. these,
Low levels of catalyst residues and amorphous polymer rates do not require costly extraction and catalyst removal steps. These high activity catalyst systems generally contain a Ziegler-Natta type polymerization catalyst which is magnesium tetrachloride supported titanium tetrachloride, a promoter which is an organoaluminum compound such as triethylaluminum, and an electron donor.

US Pat. Nos. 4,400,302 and 4,400,302
Nos. 329,253 and 4,414,132, the specification describes a combination of an organoaluminum and an electron donor that is a typical organic ester such as paraethoxyethyl benzoate, a magnesium chloride support containing an electron donor. Disclosed is a generally known third generation catalyst system containing a solid catalyst component which is titanium chloride.

Developments since the introduction of third generation catalysts have led to what is now known as fourth generation catalysts. These fourth generation catalysts are very active catalyst systems. U.S. Pat. Nos. 4,547,476, 4,829,037,
4,839,321, 4,847,227, 4,970,186, 5,066,737, 5,077,357, 5,082,907, 5 , 106,806, 5,122,494, 5,124,298, and 5,130,284 disclose fourth generation catalyst systems. These fourth generation catalyst systems are typically a solid component of magnesium chloride supported titanium tetrachloride containing an internal electron donor in combination with an organoaluminum cocatalyst, and n-propyltrimethoxysilane, phenyltriethoxysilane. , Or a known silicon compound such as cyclohexylmethyldimethoxysilane, which is known as a control factor. The improved fourth generation catalyst system uses an internal electron donor provided internally.

One special limited group of polypropylenes is the impact polypropylene. Impact polypropylene has been developed for applications requiring good room temperature and low temperature impact strength. Impact polypropylene contains a polypropylene component having finely dispersed ethylene / propylene rubber particles. Initially, these impact polypropylenes were made by compounding polypropylene and ethylene / propylene rubber. But,
The more dispersed ethylene / propylene rubber in the polypropylene matrix, the better the impact strength compared to the amount of rubber. This improved impact polypropylene manufacturing process uses ethylene / propylene in the presence of polypropylene particles.
The purpose is to polymerize propylene rubber, thereby producing impact polypropylene containing finely dispersed ethylene / propylene rubber particles in a polypropylene matrix. ChemSystem Report 1984, "World Pol
yolefin Industry ", Volume 2," Polypropylene Technol
ogy and Economics ", section 8, pages 1-20,
Discloses such a method using a two-phase reactor system. The first reactor produces polypropylene and the second reactor produces
Ethylene / propylene rubber is produced in the presence of polypropylene.

Attempts have been made to produce impact polypropylene in a gas-phase fluidized bed two-reactor system using very high activity fourth generation catalysts (activity over 20,000 g / g solid catalyst component). It has been discovered that in a gas phase fluidized bed two reactor system, the use of very high activity fourth generation catalysts produces unexpected amounts of rubber in the second reactor phase. When the amount of rubber exceeds 35% by weight, the impact strength increases, but at the same time the other properties of impact polypropylene are dramatically weakened.

[0007]

In a process using a gas phase fluidized bed dual reactor system with a fourth generation catalyst system, the rubber content in the second reactor is controlled to reduce it to less than 35% by weight. It is highly desirable to be able to. It is also highly desirable to be able to produce impact polypropylene with an improved balance of properties using this method and catalyst system.

[0008]

[Means for Solving the Problems]

(A) (a) A solid containing an internal strong electron donor produced in situ by reacting a magnesium compound suspended in the presence of an organic acid chloride with titanium tetrachloride in an organic solvent. The step of producing a substance, and the magnesium compound is represented by the following formula: MgQ _2-n X _n (wherein each Q is independently selected from an alkoxide, an aryl oxide, or a carboxylate group;
Is halogen and n is 0 or 1. ), (B) decanting, and then washing the solid substance with an organic solvent that does not dissolve the solid substance, (c) contacting the suspended solid substance with titanium tetrachloride in the organic solvent. And (d) decanting and then washing the solid material with an organic solvent that does not dissolve the solid material; (B) general formula: SiR _m (OR ′) _{4 − m} (wherein R is selected from an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, R ′ is an alkyl group, and m is 0 or an integer of 1 to 3,
When m is 2 or 3, a plurality of R groups may be the same or different, or when m is 0, 1 or 2, a plurality of R'groups may be the same or different,
And / or when R is an alkyl group, R ′ is R
A silicon compound which is the same as or different from R); (C) General formula: R ″ _n AlX _3-n (wherein R ″ is an alkyl group and X is A halogen or hydrogen atom, and n is an integer of 1 to 3, and when n is 2 or 3, a plurality of R ″ groups may be the same or different) Compounds: (D) ethers, esters, ketones, phenols, amines, amides, imines, nitriles, phosphines, phosphites, stibines, arsines,
A novel catalyst system for the vapor phase production of polypropylene comprising an external strong electron donor selected from the group of strong electron donors consisting of phosphoramides and alcoholates.

The method for producing impact polypropylene of the present invention is to produce polypropylene in the first reactor, and to produce polypropylene and (A) (B) (C) in the second reactor under the gas phase fluidized bed reactor conditions. ) And (D) in the presence of the above catalyst system, 35-90 mol% ethylene and 10
~ 65 mol% propylene is reacted, whereby
The amount of polypropylene that produced impact polypropylene and was in the second reactor during the reaction was sufficient to produce impact polypropylene containing 65-99 wt% polypropylene and 1-35 wt% ethylene / propylene rubber. , The polypropylene is selected from polypropylene homopolymers and random copolymers containing up to 5% by weight of comonomers.

The improved impact polypropylene composition of the present invention comprises: (I) a melt flow rate of 0.5 to 20 g / 10.
65-99% by weight containing at least 95% by weight propylene having a content and a xylene dissolution content of 1-6% by weight
Polypropylene and (II) 35-90 mol% ethylene and 1-35 wt% containing 10-65 mol% propylene with a unique microstructure present in less than 22% in the PEP configuration as determined by C-13 NMR.
Of an ethylene / propylene copolymer rubber of 100% by weight, the impact polypropylene composition comprising a fully polymerized blend of, and wherein the amount of rubber is less than 15% by weight, relative to the weight% rubber ratio. Having a Gardner impact strength of at least 12 and 30-6 after peroxide decomposition
It has an overall melt flow rate of 0 g / 10 min.

Alternatively, the impact polypropylene composition comprises
The composition comprises a complete polymerization blend of (I) and (II) above, wherein the rubber in the composition is at least 0.4 μm.
At least 5% of those with a cross-sectional area of m ² are in particle form. The present invention also requires a method of controlling the amount of rubber produced during the formation of impact polypropylene at constant residence time, temperature, and gas composition, and under gas phase fluidized bed reactor conditions, polypropylene and 35-90 mol% ethylene and 10-65 mol% propylene are reacted in the presence of the catalyst system, and the amount of polypropylene present in the reaction there is 65-99 wt% polypropylene and 1-35 wt% ethylene. / Polypropylene is sufficient to produce an impact copolymer and the polypropylene is selected from a polypropylene homopolymer and a random copolymer containing up to 5% by weight of comonomer, and there, an organoaluminum compound / external strong electron donation The molar ratio of the body is 0.5 and 100
Proportionally by increasing or decreasing between
Between 35 and 35% by weight, increasing or decreasing the rubber content in the polypropylene impact copolymer.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Applicants have not only discovered a process for making impact polypropylene in a gas phase fluidized bed two reactor process using an improved catalyst system and a new and improved fourth generation catalyst system, Unexpectedly, we have also discovered an improved impact polypropylene with globally balanced properties while maintaining high impact strength.

The improved impact polypropylene of the present invention is produced in a gas phase two reactor process using the improved novel catalyst system. The improved impact polypropylene of the present invention has improved impact strength while retaining standard properties or an improved balance of properties while retaining standard impact strength as compared to standard impact polypropylene. There is.

Applicants believe that the improved properties of this impact polypropylene are due to the particular particle size and shape of the ethylene / propylene rubber particles in the polypropylene matrix. The importance of having a high amount of ethylene / propylene rubber particles of a particular size is taught in the art (Fiber Reinforced RubberMod
ified Polypropyren Polymer Engneering and Science,
September 1975, Volume 15, No. 9, page 668-
672, page 670, and Propylene / ethlene-co-p
ropylene Blend Polymer, 1991, Volume 32, No.
7, pages 1186-1194, page 1193).

The novel catalyst system of the present invention for use in the gas phase formation of improved impact polypropylene comprises (A) (a) four magnesium compounds suspended in the presence of an organic acid chloride in an organic solvent. Reacting with titanium chloride to form a solid material containing an internal strong electron donor that is generated in situ, and the magnesium compound has the following formula: MgQ _2-n X _n (wherein each Q Are independently selected from alkoxide, aryl oxide, or carboxylate groups, X
Is halogen and n is 0 or 1. ), (B) decanting, and then washing the solid substance with an organic solvent that does not dissolve the solid substance, (c) contacting the suspended solid substance with titanium tetrachloride in the organic solvent. And (d) decanting and then washing the solid material with an organic solvent that does not dissolve the solid material; (B) general formula: SiR _m (OR ′) _{4 − m} (wherein R is selected from an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, R ′ is an alkyl group, and m is 0 or an integer of 1 to 3,
When m is 2 or 3, a plurality of R groups may be the same or different, or when m is 0, 1 or 2,
Provided that a plurality of R'groups may be the same or different, and / or R is an alkyl group, R'may be the same as R or different from R). Silicon compound; (C) General formula: R ″ _n AlX _3-n (wherein R ″ is an alkyl group, X is a halogen atom or a hydrogen atom, and n is an integer of 1 to 3, when n is 2 or 3, a plurality of R ″ groups may be the same or different), (D) esters, ketones, phenols, amines, amides , Imines, nitriles, phosphines,
A new catalyst system for the vapor phase production of polypropylene comprising an external strong electron donor selected from the group of strong electron donors consisting of phosphites, stibines, arsines, phosphoramides and alcoholates.

The method for producing impact polypropylene of the present invention is to produce polypropylene in the first reactor and to produce polypropylene and (A) (B) (C) in the second reactor under the conditions of gas phase fluidized bed reactor. ) And (D) in the presence of the above catalyst system, 35-90 mol% ethylene and 10
~ 65 mol% propylene is reacted, whereby
The amount of polypropylene that produced impact polypropylene and was in the second reactor during the reaction was sufficient to produce impact polypropylene containing 65-99 wt% polypropylene and 1-35 wt% ethylene / propylene rubber. , The polypropylene is selected from polypropylene homopolymers and random copolymers containing up to 5% by weight of comonomers. (A)
The magnesium compound used to produce the solid catalyst compound of 1. is preferably suspended in an organic solvent before reacting in step (a). Suspending the magnesium compound before contacting the organic acid chloride and titanium tetrachloride ensures a more complete reaction. The amount of magnesium compound suspended in the organic solvent is preferably 2 to 20% by weight, more preferably 5 to 15% by weight, and most preferably 10% by weight.

The organic solvent can be any organic solvent that does not dissolve magnesium chloride. Suitable organic solvents are
Including an aromatic or aliphatic organic solvent, and an aromatic or aliphatic halohydrocarbon solvent, preferably,
It is an aromatic solvent or an aromatic halohydrocarbon solvent. Examples of suitable specific solvents include benzene, chlorobenzene, and toluene, with toluene being most preferred.

Preferred magnesium compounds within the above formula are alkoxy and arylalkoxy magnesium halides; magnesium dialkoxides, magnesium diaryl oxides; magnesium alkoxide carboxylates; magnesium aryl oxide carboxylates; and magnesium alkoxide aryl oxides. Is selected from the group consisting of kinds. Specific examples of suitable magnesium compounds include isobutoxy magnesium chloride, ethoxy magnesium bromide, phenoxy magnesium iodide, cumyloxy magnesium bromide, naphtheneoxy magnesium chloride, magnesium di-isopropoxide, magnesium diethoxide, Magnesium dibutoxide, magnesium diphenoxide, magnesium dinaphthene oxide, ethoxy magnesium isobutoxide, magnesium dioctanoate, magnesium dipropionate, ethoxy magnesium phenoxide, naphthene oxide magnesium isoamyl oxide, ethoxy magnesium octanoate, phenoxy magnesium propionate , And chloromagnesium dodecanoate, due to availability and cost. Neshi um diethoxide is most preferred. During the reaction in (a), the strong electron donor of (a)
When prepared from organic acid chloride precursors, the magnesium compound should have at least one OR group, with magnesium alkoxides or alkoxy magnesium chlorides being preferred.

The internal strong electron donor of (a) is preferably an ester, prepared in situ from the corresponding organic acid chloride. The internal electron donor is preferably prepared in situ by reaction with a magnesium compound such as an organic acid chloride precursor magnesium alkoxide.
The preferred organic acid chloride precursor used to prepare the internal strong electron donor of (a) is a chloride that reacts with diethoxymagnesium to produce the most preferred internal strong electron donor of ethyl benzoate and diethyl phthalate. It is selected from benzoyl and phthaloyl dichloride.

The term "strong electron donor", as used herein, means that the compound is a Lewis base compound and has an active catalytic site for receiving an electron, such as titanium trichloride, to form a strong complex. It has a strong electron donating property. In the catalyst system prepared and used according to the present invention,
The internal strong electron donor of the solid catalyst compound of (A) is (a)
In the reaction for producing the organic acid chloride precursor of 0.1 to 2 mol per mol of the magnesium compound, more preferably 0.2 to 0.4 mol per mol of the magnesium compound.

When the solid catalyst component (A) is prepared, titanium tetrabasic is preferably present in (a) in an amount of 2 to 6 mol per mol of the magnesium compound, and 3 to 4 mol per mol of the magnesium compound. More preferable.
In (a), the amount of titanium tetrachloride far exceeding 6 mol per mol of the magnesium compound exceeds the amount necessary for effective production of magnesium chloride, and An amount of less than 2 moles titanium tetrachloride per unit requires more titanium tetrachloride in step (c) or in many iterations of step (c).

The solid material prepared in (a) needs to be removed from the solvent by decanting and then washed to remove unreacted components. This wash is
It is performed using an organic solvent that does not dissolve the solid substance. Suitable examples of such organic solvents include those in (a) above. This washing step of (b) can be repeated as many times as necessary to sufficiently remove by-products, impurities or unreacted components.

The prepared, washed and decanted solid material is again suspended in the organic solvent and treated with titanium tetrachloride for at least more than 1 hour. This process
It can be done once or several times, as long as a sufficient amount of the magnesium compound is converted to magnesium chloride and a sufficient amount of titanium tetrachloride is deposited on the surface of the magnesium chloride in the solid material. After each treatment with titanium tetrachloride or after the final treatment, the solid material is decanted again and washed with organic solvent. Each wash can be performed as many times as necessary to remove unwanted material, but is preferably at least three times. After the washing step (d), the titanium tetrachloride treatment step (c) is preferably repeated at least twice and then washed again. Titanium tetrachloride in the initial or subsequent contacting step has a concentration of 200 to 600 mmol in 100 ml of an organic solvent and a molar ratio of 2 to 6 mol per mol of magnesium, and more preferably 1 mol of magnesium compound. At a molar ratio of 4 to 5 mol per unit, 400 to 500 m / mol is more preferable.

The solid catalyst component (A) is preferably prepared under stirring at a temperature of 80 to 125 ° C. for 30 minutes to 8 hours, and most preferably at a temperature of 100 to 110 ° C. for 2 to 3 hours. At temperatures below 80 ° C., the preparation of the solid catalyst component begins relatively slowly, whereas
At temperatures above 25 ° C, the solvent begins to evaporate at atmospheric pressure. Times shorter than 30 minutes are probably not sufficient to complete the reaction, whereas times longer than 8 hours are not necessary.

The catalyst system according to the present invention requires the presence of a silicon compound of the above formula. Examples of suitable silicon compounds are tetraalkoxysilanes, alkylalkoxysilanes, phenylalkoxysilanes, phenylalkylalkoxysilanes, cycloalkylalkoxysilanes, cycloalkylalkylalkoxysilanes,
Includes cycloalkylphenylalkoxysilanes, and cycloalkylalkylphenylalkoxysilanes. Examples of specific silicon compounds are tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, dimethyldimethoxysilane, triethylmethoxysilane, trimethylmethoxysilane, diethyldiethoxy. Silane, diisobutyldimethoxysilane, propyltrimethoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxy Silane, triphenylmethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane Emissions, dicyclopentyldimethoxysilane, tricyclohexyl ethoxysilane,
Includes phenyl (methyl) -dimethoxysilane, cyclohexyl (ethyl) phenylmethoxysilane, dicyclohexyldiethoxysilane, vinyltrimethoxysilane, vinyl (dimethyl) methoxysilane, and vinyl (cyclohexyl) methylmethoxysilane, including cyclohexylmethyldimethoxysilane and Phenyltriethoxysilane is most preferred.

The amount of the silicon compound (B) in the catalyst system of the present invention is an amount that produces an organic aluminum compound molar ratio of 1 to 200, preferably 3 to 25, relative to the silicon compound, and an organic compound / silicon compound molar ratio of 5 ~ 15
Most preferred. Organic aluminum smaller than 1 /
Molar ratios of silicon compounds give rise to low catalytic activity, whereas molar ratios much higher than 200 produce polypropylenes with undesirably high xylene solubility.

The organoaluminum compound (C) is preferably selected from the group consisting of trialkylaluminums, dialkylaluminum halides, and dialkylaluminum hydrides. Preferred organoaluminum compounds are selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, and diisobutylaluminum hydride,
Triethylaluminum (TEAL) is most preferred due to availability and cost.

The organoaluminum compound has a molar ratio of organoaluminum compound / titanium of 25 to 300, preferably,
An amount that produces 50 to 150 is preferred, with an organoaluminum compound / titanium molar ratio of 50 to 100 being most preferred. Molar ratios of organoaluminum compound / titanium lower than 25 result in catalyst systems with very low catalytic activity, whereas molar ratios higher than 300 are not necessary.

The external strong electron donor of (D) is preferably selected from the group of strong electron donors consisting of esters and amines, but from the viewpoint of availability and cost, esters are most preferable. Examples of suitable esters and amines are ethyl benzoate, methyl benzoate, p
-Methoxyethyl benzoate, p-ethoxymethyl benzoate, p-ethoxyethyl benzoate, ethyl acrylate, methyl methacrylate, ethyl acetate, dimethyl carbonate, dimethyl oxalate, p
-Chloroethyl benzoate, p-aminohexyl benzoate, isopropyl naphthalate, n-amyl toruate, ethyl cyclohexanoate, propyl pivalate, N, N, N ', N'-tetramethylethylenediamine, 1,2,4-trimethylpiperazine , 2, 3,
4,5-Tetraethylpiperidine, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-t-butyl phthalate, diisoamyl phthalate, di-t-amyl phthalate , Dineopentyl phthalate, di-2-ethylhexyl phthalate, and di-2-ethyldecyl phthalate. The most preferred external strong electron donor is p-
Ethoxyethyl benzoate (PEEB).

The external strong electron donor (D) used in the catalyst system of the present invention is preferably an amount which gives an organoaluminum compound / external strong electron donor molar ratio of 0.5 to 100, more preferably 1 to 10. It is more preferably present and most preferably an organoaluminum compound / external electron donor molar ratio of 1-4. Molar ratios of organoaluminum compounds / external electron donors of less than 0.5 lead to lower levels of catalyst activity to undesired levels, whereas molar ratios of more than 100 result in ethylene / propylene rubber formation. , Not significantly reduced.

The term "external strong electron donor" as used herein refers to a reaction mechanism in which the strong electron donor is not part of the solid catalyst compound, but controls the formation and quality of the rubber moiety. , Still means to play an important role. In the catalyst system according to the present invention, the reactant of the solid catalyst compound (A) is preferably magnesium dichloride 6
0 to 85% by weight, titanium tetrachloride 5 to 15% by weight, and external strong electron donor 10 to 25% by weight, more preferably magnesium dichloride 68 to 77% by weight, titanium tetrachloride 8 to 12% by weight. %, And external strong electron donor 15 to
An amount of 20% by weight.

The process for producing impact polypropylene according to the invention in a second reactor of a two-reactor system under gas phase fluidized bed reactor conditions is preferably carried out under the following conditions: temperature 45-90 ° C. Pressure 200-550psi (1,378
~ 3,790 kPa), layer weight 50-120 pounds (2
2 to 55 kg), circulating gas flow 15,000 to 25,000
0 lb / hr (6,810-11,350 kg / hr),
Residence time 50 to 200 minutes, propylene concentration 10 to 75 mol% (relative to total gas amount), hydrogen / propylene molar ratio 0.0015 to 0.40, ethylene / propylene molar ratio 0.45 to 2.5, catalyst Feeding 0.5 to 3 cc / hour (concentration of solid catalyst (A) in carrier is 10 to 50% by weight)
In the case of), the titanium concentration is 0.13 to 2.16% by weight (based on the total catalyst slurry), the organoaluminum compound / silicon compound molar ratio is 1 to 150, the organoaluminum compound / titanium molar ratio is 25 to 300, and the organoaluminum compound. / External strong electron donor molar ratio 0.5 to 100.

In the process for producing impact polypropylene according to the invention in a two-reactor system, the polypropylene precursor is
The following conditions: temperature 45 to 95 ° C, pressure 250 to 700p
si (1,723-4,823 kPa), layer weight 35-
130 lbs (16-59 kg), circulating gas flow 15,0
00-25,000 lb / hr (6,810-11,3
50 kg / hour), residence time 50-200 minutes, propylene concentration 50-98 mol% (relative to total gas amount), hydrogen / propylene molar ratio 0.001-0.2, catalyst supply 0.5-
3 cc / hr (the concentration of solid catalyst (A) in the carrier is
In the case of 10 to 50% by weight), the titanium concentration is 0.13 to 2.
16 wt% (relative to total catalyst slurry), organoaluminum compound / silicon compound molar ratio 1-150, organoaluminum compound / titanium molar ratio 25-300, prepared in the first reactor, and polypropylene Send to two reactors.

These process conditions are 80 to 150 f.
It is understood that it is only preferred in reactors having a volume of about 100 ft ³ (2,830 liters), such as reactors in the volume range of t ³ (2,264-4,245 liters). For larger scale reactors, certain process conditions such as bed weight, catalyst feed, circulating gas flow, residence time, propylene concentration, etc. will vary.

The process according to the invention comprises 35 to 90 mol% ethylene and 10 to 65 mol% propylene, preferably 45 to 90 mol% ethylene and 10 to 55 mol%.
Carried out in the presence of propylene, the mol% of ethylene and propylene being 50-65 and 50-3, respectively.
Most preferably, it is 5%. Ethylene below 35 mol% or above 90 mol% does not produce rubber which is a good impact modifier. The amount of propylene present during the reaction is preferably from 30 to 6 of the total gas amount.
It is 0 mol%.

The amount of polypropylene sent from the first reactor of the two-reactor process to the second reactor is 65 to 99% by weight, and 1 to 35% by weight of ethylene / propylene rubber is produced in the second reactor. To be done. Amounts of ethylene / propylene rubber below 1% by weight do not significantly improve the impact strength of impact polypropylene, while 35% by weight
Even higher amounts of ethylene / propylene rubber increase impact strength, but dramatically reduce other properties of impact polypropylene. The amount of rubber produced in the second reactor is preferably 5 to 30% by weight, more preferably 1
0 to 25% by weight, ethylene / propylene rubber 10
-20% by weight is most preferred.

The impact polypropylene composition of the present invention comprises:
(I) 65-99 wt% polypropylene containing at least 95 wt% propylene having a melt flow rate of 0.5-20 g / 10 min and a xylene dissolution content of 1-6 wt%,
And (II) 35-90 mol% ethylene and C-1
22% in PEP configuration determined by 3 NMR
10-65 mol% with a unique microstructure present below
An impact polypropylene composition comprising a complete polymerization blend of 1 to 35 wt% ethylene / propylene copolymer rubber containing propylene, wherein the amount of rubber is 15%.
When less than wt%, it has a Gardner impact strength of at least 12 wt% rubber ratio and an overall melt flow rate of 30-60 g / 10 min after peroxide decomposition.

The impact polypropylene prepared according to the present invention is unique and has an overall improved balance of properties at the impact strength obtained. The impact polypropylene exhibits improved Gardner impact strength (i.e., at least 12) relative to the weight percent rubber ratio (when the amount of rubber is less than 15 weight percent). More preferably, this ratio is at least 15 when the amount of rubber is less than 15% by weight.

It is believed that the impact polypropylene composition according to the present invention exhibits an overall improved balance of physical properties due to the unique microstructure of the ethylene / propylene rubber particles in the propylene matrix. The rubber of the entire composition of the present invention is in the form of particles and has at least 5
% Has a cross-sectional area of at least 0.4 μm ² . To make this measurement, tensile test specimens are cut to expose the surface and the rubber particles are dissolved by extraction with xylene, after which the surface is observed under a scanning electron microscope to measure the particles. The surface of the impact polypropylene of the present invention is shown in a micrograph Fig. 2. The rubber in the composition of the present invention preferably comprises at least 5% 0.4 and 1 μm ^2.
With a cross-sectional area between (at least 8 with this cross-sectional area
% Particle is the most preferred) particle shape.

For many unique molding applications, the overall melt flow rate after peroxide decomposition is preferably 30-60 g.
/ 10 minutes, with 30 to 45 g / 10 minutes being most preferred. Polypropylene of (I) is 0.5 to 20 g / 10
It has a melt flow rate of minutes, preferably from 1 to 10 g / 10 minutes, most preferably from 1.5 to 3 g / 10 minutes. 1
Polypropylene with a melt flow rate well below g / 10 min produces fractional melt flow impact polypropylene and is difficult to pelletize with an underwater cutter at a melt flow rate of 30-60 g / 10 min after peroxide decomposition. . Polypropylene having a melt flow rate of more than 20 g / 10 min has a relatively high melt flow rate of 15 g / 10 min with a poor performance balance at a melt flow rate of 30-60 g / 10 min after peroxide decomposition. Produces polypropylene.

The polypropylene of (I) contains 1 to 6% by weight.
Xylene dissolution content, preferably 1.2-4.5% by weight
Most preferably from 1.5 to 2% by weight.
Polypropylene with a xylene solubility (Xsc) below 1 is difficult to produce, whereas polypropylene with an Xsc above 6% by weight is undesirably low rigidity (modulus). Indicates.

The ethylene / propylene copolymer rubber of (II) has a unique microstructure with less than 22% present in the PEP composition as determined by C13 NMR. This means that the unblocked ethylene between adjacent polypropylenes in the polymer chain is less than 22% of the total ternary distribution. More preferably, the amount of rubber with PEP composition is less than 20%. Ethylene / propylene copolymer rubber fractions with PEP composition above 22% are not desirable and preferred sizes (0.4-1.0 μm ² ).
It does not have significant blocked ethylene to produce rubber particles.

Another important advantage of the present invention is the ability to control the amount of rubber produced during the formation of impact polypropylene at constant residence time, temperature and gas composition. This method of controlling the amount of rubber is based on polypropylene and (A) (B) (C) under gas phase fluidized bed reactor conditions.
35-90 above in the presence of a catalyst comprising (D)
Comprising reacting mol% ethylene and 10-65 mol% propylene, and the amount of polypropylene present during the reaction comprises 65-99 wt% polypropylene and 1-35 wt% ethylene / propylene rubber. An amount sufficient to produce impact polypropylene, said polypropylene being selected from a polypropylene homopolymer and a random copolymer containing up to 5% by weight of comonomer, and an organoaluminum compound / external strong electron donor mole. The ratio is raised and lowered between 0.5 and 100 and proportionally increases and decreases the rubber content in the impact polypropylene between 1 and 35% by weight. The organoaluminum compound / external strong electron donor molar ratio can be raised or lowered between 0.5 and 100 and the rubber content can be increased or decreased proportionally between 1 and 35% by weight. Molar ratios outside this range are undesirable as described above. This organoaluminum / external strong electron donor molar ratio is preferably raised or lowered between 1 and 5 to increase or decrease rubber production. The organoaluminum compound / external strong electron donor molar ratio is raised or lowered by injecting the desired amount of external strong electron donor in the carrier into the reactor.

The following example illustrates the invention but is not intended to limit the reasonable scope of the invention.

[0045]

EXAMPLES General Gas Phase Process A continuous gas phase reactor was used for the production of polypropylene powder. All gas components were purified to remove known catalyst poisons. The gas composition of polypropylene was maintained at 75 mol%. The hydrogen concentration was varied to produce the desired melt flow rate polypropylene. The remaining gas composition consisted of nitrogen and small amounts of inert impurities. The reactor bed temperature was maintained at 67 degrees. Total pressure is 535 psi (3,686 kP
It was a). The bed was fluidized by maintaining a circulating gas flow of 19,000 pounds / hour. The catalyst was continuously fed to the reactor. TEAL was fed continuously as a dilute solution in isopentane (2.0% TEAL). The TEAL / Ti molar ratio was maintained between 60-65. The electron donor (PEEB) was fed continuously as a dilute solution in isopentane (1% PEEB). TEA
The desired product was prepared by maintaining the L / PEEB molar ratio between 2.1 and 2.6. Periodically, polypropylene powder was discharged from the reactor to properly maintain a constant bed weight of 75 pounds. The powder was quenched with steam.

Third Generation Catalyst System The third generation solid catalyst component used in the comparative example was a TiCl ₄ supported on a strong internal electron donor ester and MgCl _2.
It was prepared by reacting magnesium diethoxide with titanium tetrachloride in the presence of a strong internal electron donor ester to give a solid component containing. The solid catalyst component includes about 70 wt% MgCl ₂ and about 10 wt% TiCl ₄ ,
The rest were internal strong electron donor esters. The solid catalyst component was used in combination with TEAL catalyst and PEEB. Specific amounts and molar ratios are given in the examples.

Fourth Generation Catalyst System The fourth generation solid catalyst component (A) used in this example was prepared as described in the specification. The preparation of the third generation catalyst component is different in that magnesium diethoxide is reacted with titanium tetrachloride, a strong internal electron donor precursor, an organic acid chloride and phthaloyl dichloride. As a result, about 70% by weight
A solid catalyst component (A) was produced which was MgCl ₂ and about 10 wt% TiCl ₄ , the balance being an in situ prepared internal strong electron donor ester, diethyl phthalate. In the unmodified fourth generation catalyst system, component (A) is used in combination with TEAL and CHMDS in the amounts and molar ratios specified in the examples.

Polymer Properties Standard analytical test methods were used to characterize impact polypropylene and homopolypropylene precursors. Melt flow rates were measured using ASTM test method D-1238-85. The xylene dissolution content (Xsc) was determined by dissolving the polymer in refluxing xylene, cooling the solution to 25 ° C. for crystallization, filtering the slurry, evaporating the solvent and calibrating the residue. Amorphous rubber content, 150 ℃
Dissolve the polymer in a 90/10 solvent mixture of mineral spirits and diethylene glycol monobutyl ether at room temperature, crystallize the solution by cooling to room temperature, filter the slurry, precipitate the amorphous polymer by adding acetone to the solution, And it measured by isolating it. Ethylene content (Et) of the total polymer, rubber content (Rc), and ethylene content of the rubber part (E
f) was measured by infrared spectroscopy. Impact polypropylene is Arburg 30 according to ASTM conditions
Injection molding was performed on a 5S molding machine. Physical properties were obtained using standard test methods (see Table I).

[0049]

[Table 1]

C-13 NMR analysis A solution of amorphous ethylene-propylene copolymer rubber (volume ratio 10% by weight) was used as an internal standard of 20% benzene-
Prepared in o-dichlorobenzene containing D6. Proton decouple C-13 NMR spectrum, 67.5M
Recorded on a JEOL-270 spectrometer operating at Hz.
The probe temperature was set to 120 ° C. C-13 spectra were recorded with a long delay (20 seconds) between 90 pulses to avoid differential saturation of the peaks, which gives quantitative information. Gate decoupling was used to eliminate possible differences in nuclear Overhauser effect contributions.
Chemical shifts were 2.03 ppm and referenced to hexamethyldisiloxane. The spectral range is Hare Res
Determined by curve deconvolution using FTNMR software by earch. For curve analysis, the line width and peak height were varied until they were well fitted. Therefore,
Information about the ordinal distribution was obtained using the determined component peaks. Peak allocation is consistent with many current polyolefin NMR studies, Kakugo (Kakug).
Macromol 15, 1150, 1982, et al.
(See reference).

Scanning Electron Microscope Sample Preparation Samples were prepared from tensile specimens molded using a Reichert S Ultramicrotome. The cutting conditions are as follows: diamond knife set 35 ° C., knife clearance 6 °, knife temperature −90 ° C., sample temperature −90 ° C., and sample cross section area 0.5 mm × 1 mm.

After the surface was prepared with a microtome, the sample was touched in xylene at 26 ° C. for 10 minutes and placed in an ultrasonic bath for 10 minutes to remove the xylene-dissolved rubber phase. The samples were rinsed with acetone, air dried, and then gold coated for 40 seconds in a sputter coater Pelco SC4. Electron microscope scanning of the surface
Cambridge S-260 Scanni with a second electronic detector
Obtained by ng Electron Microscope (SEM). Working distance 1
All micrographs were obtained at ˜4,000 magnification using 0 mm and accelerating voltage of 10 KV. The photomicrographs obtained from this technique yielded a solid polypropylene matrix with holes in the places where the rubber particles were originally present. These micrographs were then analyzed to give information regarding the amount of rubber particles. Micrographs of three different impact polypropylenes are presented in Figures 1, 2 and 3.

Examples 1 to 3 (Comparative) The continuous gas phase reactor described above was operated in a dual reactor mode (with two reactors in series). The first reactor, which produces polypropylene, has a TEAL / PEEB molar ratio of 2.
5, a solid MgCl ₂ supported TiCl ₄ catalyst containing internal strong electron donor ester, TEAL, and PEEB at a TEAL / Ti molar ratio of 65, a temperature of 67 ° C., and a hydrogen / propylene molar ratio of 0.0045. Operated with 3rd generation catalyst. See Table II for other reactor conditions. Under these conditions, a production rate of 20 pounds (9.1 kg) / hour and a catalytic activity of 4,800 g / g solid catalyst, a melt flow rate of 0.60 g / 10 min, an Xsc of 3.8.
% Polypropylene and a residual Ti content of 5.2 ppm was produced. Polypropylene powder containing the active catalyst was periodically transferred from the first reactor to the second reactor in order to maintain a proper constant bed weight of 75 pounds (34 kg). The second reactor was operated under the conditions of Table II. The catalyst transferred with polypropylene powder from the first reactor to the second reactor is almost inert for rubber production,
Ethylene / propylene rubber fraction (Rc) 14 and 20
% TE had to be rejuvenated with additional TEAL (Examples 2 and 3) to produce impact polypropylene.

[0054]

[Table 2]

Examples 4-5 (Comparative) The continuous gas phase reactor described above was operated in a dual reactor mode (with two reactors in series). The first reactor was fitted with the above solid catalyst composition (A) (MgCl ₂ -supported TiC).
l ₄ and containing internal strong electron donor is prepared in the original location), together TEAL / CHMDS mole ratios 5, TEA
TEAL (C) and CH at an L / Ti molar ratio of 100, a temperature of 67 ° C. and a hydrogen / propylene molar ratio of 0.0040.
It was run with an unmodified 4th generation catalyst containing MDS (B). See Table III for other reactor conditions. Under these conditions, a production rate of 30 pounds (13.6 kg)
/ H and catalytic activity 16,500 g / g solid catalyst produced polypropylene with a melt flow rate of 2.1 g / 10 min, Xsc of 1.5% and a residual Ti content of 1.5 ppm. Polypropylene powder containing an active catalyst was added to maintain a proper constant bed weight of 75 pounds (34 kg).
Periodically transferred from the first reactor to the second reactor. The second reactor was operated under the conditions of Table III. The results showed that the impact polypropylene produced under normal conditions contained an excess of rubber (hence undesirable). Impact polypropylene containing excess rubber (greater than 35%) exhibits very low stiffness and is difficult to process due to stickiness. Because the conditions used to control the rubber content Rc in Example 5 are low propylene concentration, low temperature, and low bed weight, commercial processes operating under such odd conditions are uneconomical and impractical. Therefore, it is not acceptable.

[0056]

[Table 3]

Examples 6-8 These examples illustrate the advantages of a modified fourth generation catalyst system with an external strong electron donor in the second reactor producing ethylene / propylene rubber. Using the fourth generation catalysts of Examples 4 and 5, except modified by adding PEEB to Reactor 2, a continuous gas phase polypropylene reactor was operated in a dual reactor mode to provide a rubber content of Impact polypropylene with 10-20% was produced. See Table IV for conditions and results. Examples of these are solid ingredients,
It is shown that an external strong electron donor PEEB in combination with an organoaluminum compound and a defined fourth generation catalyst system containing a silicon compound can be used to successfully produce good impact polypropylene. Therefore,
Impact polypropylene in the effective rubber content range can be produced in the gas phase reactor according to the invention using the fourth generation catalyst of the invention operating under normal conditions.

[0058]

[Table 4]

Example 9 Table V below represents a comparison of the physical properties of some impact polypropylenes.

[0060]

[Table 5]

This physical property data shows that impact polypropylene produced according to the present invention using the catalyst of the present invention shows a significant improvement in physical property balance over the physical properties of impact polypropylene produced using a commercial third generation catalyst. Represent something. Amorphous rubber is rarely needed to achieve some level of impact strength, thus flexural modulus, tensile strength, Vicat softening point, and heat deflection temperature are maintained at higher levels. . Example 2 and Example 6 and Example 3 and Example 7 are compared. The improved physical property balance is of great interest to plastic manufacturers and consumers as it results in material cost savings and performance improvements.

Example 10 Three percent amorphous rubber content of impact copolymer by NMR analysis
C-13 NMR of the non-crystalline part of the original distribution of the four impact copolymers
Was measured. The ternary distribution of ethylene is shown in Schedule VI.
The amorphous rubber percentage of the impact copolymers produced using the impact polypropylene purchased from Himont under the name Himont SD 242 and the third generation catalyst (Example 2) is based on the PEP present.
It has similar amounts of (ethylene between two propylenes), EEP (two ethylenes together), and EEE (one row of three ethylenes) type structures. However, the amorphous rubber percentage of the two impact copolymers (Examples 6 and 7) produced by the catalyst of the present invention is significantly less than the other two examples, PEP along the chain (ie, isolated ethylene). Have quantity. At the same time, EEP and EEE
Higher (ie blocked ethylene). Although the enhanced performance of the two impact copolymers produced using the catalyst of the present invention is found to be due to the difference in the microstructure of the amorphous rubber portion (ie the large proportion of blocked ethylene in this polymer portion). It was surprising.

[0063]

[Table 6]

Example 11 Determination of rubber particle size and distribution using a scanning electron microscope
Quantitative analysis micrographs were analyzed using Featurescan software. Micrographs were collected from 5 different areas of each sample and images for quantification were obtained and averaged. Image processing was performed on a Link eXL Energy Dispersive X-Ray spectroscopy system with image acquisition hardware and Featurescan software.

FIGS. 1, 2 and 3 show Himont S, respectively.
D 242, impact polypropylene made according to the invention in Example 7 and impact polypropylene made with a third generation catalyst according to Example 2. Significant morphological differences are seen. FIG. 1 represents a large number of large holes. FIG. 2 represents a relatively uniform particle distribution with spherical holes. FIG. 3 represents many small holes and holes with irregular shapes.

Himont material (FIG. 1) is 0.4-1 μm
Impacted polypropylene made according to the invention in Example 7 with 4% particles of ² sizes (particle cross-sectional area) has the same range of particles with 8.3%, but in Example 2 with the third generation catalyst. Impact-made polypropylene made up 3.6% of the particles in this size range. Table VII summarizes the particle distribution for the three cases. Because the physical properties of the three impact polypropylenes show the best balance of physical properties, the impact polypropylenes prepared according to the invention with the catalysts of the invention must have a favorable rubber particle size and distribution for impact toughening. Show.

[0067]

[Table 7]

[Brief description of drawings]

FIG. 1 is a micrograph showing the surface of particles of impact polypropylene commercially available as Himont SD 242 from Himont USA Inc. Dimples are voids left where ethylene propylene rubber particles were present in the solid polypropylene matrix.

2 is a micrograph showing the surface of impact polypropylene particles prepared according to the present invention in Example 7. FIG.

FIG. 3 is a micrograph showing the surface of impact polypropylene particles prepared according to the prior art in Example 2.

Front Page Continued (72) Inventor Reboy Boyder Hate United States, Texas 75601, Longview, Honeysuckle Lane 26 (72) Inventor Lewis Angel Pergan United States, Texas 75604, Longview, Creekside Drive 38 (72) Inventor Kimberley Linney Pain United States, Texas 75605, Longview, 704, Judson Road 2810 (72) Inventor Jeffrey James Vanderbilt United States, Texas 75604, Longview, Woodhollow Court 2403

Claims (36)

[Claims] 1. An internal strong electron donor produced in situ by reacting (A) (a) a magnesium compound suspended in the presence of an organic acid chloride in an organic solvent with titanium tetrachloride. The step of producing a solid substance containing a body, and the magnesium compound has the following formula: MgQ _2-n X _n (wherein each Q is independently selected from an alkoxide, an aryl oxide, or a carboxylate group. , X
Is halogen and n is 0 or 1. ), (B) decanting, and then washing the solid substance with an organic solvent that does not dissolve the solid substance, (c) contacting the suspended solid substance with titanium tetrachloride in the organic solvent. And (d) decanting and then washing the solid material with an organic solvent that does not dissolve the solid material; (B) general formula: SiR _m (OR ′) _{4 − m} (wherein R is selected from an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, R ′ is an alkyl group, and m is 0 or an integer of 1 to 3,
When m is 2 or 3, a plurality of R groups may be the same or different, or when m is 0, 1 or 2, a plurality of R'groups may be the same or different,
And / or when R is an alkyl group, R ′ is R
A silicon compound which is the same as or different from R); (C) General formula: R ″ _n AlX _3-n (wherein R ″ is an alkyl group and X is A halogen or hydrogen atom, and n is an integer of 1 to 3, and when n is 2 or 3, a plurality of R ″ groups may be the same or different) Compounds: (D) ethers, esters, ketones, phenols, amines, amides, imines, nitriles, phosphines, phosphites, stibines, arsines,
A catalyst system for the vapor phase production of polypropylene comprising an external strong electron donor selected from the group of strong electron donors consisting of phosphoramides and alcoholates. 2. A catalyst system according to claim 1, wherein the magnesium compound is suspended in an organic solvent and is 5 to 15% by weight before step (a). 3. The magnesium compound is isobutoxy magnesium chloride, ethoxy magnesium bromide, phenoxy magnesium iodide, cumyloxy magnesium bromide, naphtheneoxy magnesium chloride, magnesium di-isopropoxide, magnesium diethoxide, magnesium dibutoxide, magnesium. Diphenoxide, magnesium dinaphthene oxide, ethoxy magnesium isobutoxide, magnesium dioctanoate, magnesium dipropionate, ethoxy magnesium phenoxide, naphthene oxide magnesium isoamyl oxide, ethoxy magnesium octanoate, phenoxy magnesium propionate, and chloro magnesium dodeca. The catalyst system of claim 1 selected from the group consisting of noates. 4. The external strong electron donor is ethyl benzoate, methyl benzoate, p-methoxyethyl benzoate, p-ethoxymethyl benzoate, p-ethoxyethyl benzoate, ethyl acrylate, methyl methacrylate, ethyl acetate, dimethyl carbonate, dimethyl oxa. Rate, p-chloroethyl benzoate, p-aminohexyl benzoate, isopropyl naphthalate, n-amyltoluate, ethylcyclohexanoate, propyl pivalate, N, N, N ′,
N'-tetramethylethylenediamine, 1,2,4-trimethylpiperazine, 2,3,4,5-tetraethylpiperidine, dimethylphthalate, diethylphthalate,
Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-t-butyl phthalate, diisoamyl phthalate, di-t-amyl phthalate, dineopentyl phthalate, di-2-ethylhexyl phthalate, And J-
The catalyst system of claim 1 selected from the group consisting of 2-ethyldecyl phthalate. 5. The catalyst system according to claim 1, wherein the internal strong electron donor of (a) is an ester formed in situ by reacting an organic acid chloride with a magnesium alkoxide. 6. The internal strong electron donor of (a) is selected from the group consisting of ethyl benzoate and diethyl phthalate produced by reacting benzoyl chloride or phthaloyl dichloride with diethoxymagnesium. Catalyst system. 7. The internal strong electron donor in the solid catalyst component of (A) is an organic acid chloride precursor in (a) in an amount of 0.2 to 0.4 mol per mol of the magnesium compound. A catalyst system according to claim 1, which is present in the form during the reaction. 8. The amount of titanium tetrachloride present in (a) is
The catalyst system according to claim 1, which is 3 to 4 mol per mol of the magnesium compound. 9. The amount of titanium tetrachloride added to 100 ml of an organic solvent containing a suspended solid substance in (c) is
The catalyst system according to claim 1, having a concentration ratio of 400 to 500 m / mol and a concentration of 4 to 5 mol per mol of the magnesium compound. 10. The catalyst system according to claim 1, wherein the molar ratio of organoaluminum compound / external strong electron donor is 1 to 10. 11. The catalyst system of claim 1, wherein step (c) is repeated after at least one washing step (d). 12. The steps (a), (b) and (c) of (A).
The catalyst system according to claim 1, wherein and (d) are carried out at a temperature of 100 to 110 ° C. under stirring for 2 to 3 hours. 13. The silicon compound (B) is tetraalkoxysilanes, alkylalkoxysilanes, phenylalkoxysilanes, phenylalkylalkoxysilanes, cycloalkylalkoxysilanes, cycloalkylalkylalkoxysilanes, cycloalkylphenyl. The catalyst system of claim 1 selected from the group consisting of alkoxysilanes and cycloalkylalkylphenylalkoxysilanes. 14. The silicon compound (B) is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, dimethyldimethoxysilane, triethylmethoxysilane, trimethylmethoxysilane. , Diethyldiethoxysilane, diisobutyldimethoxysilane, propyltrimethoxysilane,
Ethyltrimethoxysilane, ethyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane, cyclohexyltriethoxysilane , Cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, tricyclohexylethoxysilane, phenyl (methyl) -dimethoxysilane, cyclohexyl (ethyl) phenylmethoxysilane, dicyclohexyldiethoxysilane, vinyltrimethoxysilane,
14. The catalyst system of claim 13 selected from the group consisting of vinyl (dimethyl) methoxysilane and vinyl (cyclohexyl) methylmethoxysilane. 15. The silicon compound of (B) is 1 to 20.
The catalyst system of claim 1 present in an amount that results in an organoaluminum compound molar ratio to silicon compound of zero. 16. The organoaluminum compound of (C) is
The catalyst system of claim 1 selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, and diisobutylaluminum hydride. 17. The organoaluminum compound is 50 to 1
A catalyst system according to claim 1 present in an amount which results in an organoaluminum compound molar ratio to titanium of 50. 18. A step of producing polypropylene in the first reactor, and in the second reactor, under the conditions of a gas phase fluidized bed reactor, polypropylene, and (A) (a) an organic acid salt in an organic solvent. Reacting a magnesium compound suspended in the presence of a substance with titanium tetrachloride to produce a solid material containing an internal strong electron donor formed in situ, and said magnesium compound having the formula: MgQ _2-n X _n (wherein each Q is independently selected from an alkoxide, an aryl oxide, or a carboxylate group, and X
Is halogen and n is 0 or 1. ), (B) decanting, and then washing the solid substance with an organic solvent that does not dissolve the solid substance, (c) contacting the suspended solid substance with titanium tetrachloride in the organic solvent. And (d) decanting and then washing the solid material with an organic solvent that does not dissolve the solid material; (B) general formula: SiR _m (OR ′) _{4 − m} (wherein R is selected from an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, R ′ is an alkyl group, and m is 0 or an integer of 1 to 3,
When m is 2 or 3, a plurality of R groups may be the same or different, or when m is 0, 1 or 2, a plurality of R'groups may be the same or different,
And / or when R is an alkyl group, R ′ is R
A silicon compound which is the same as or different from R); (C) General formula: R ″ _n AlX _3-n (wherein R ″ is an alkyl group and X is A halogen or hydrogen atom, and n is an integer of 1 to 3, and when n is 2 or 3, a plurality of R ″ groups may be the same or different) Compounds: (D) ethers, esters, ketones, phenols, amines, amides, imines, nitriles, phosphines, phosphites, stibines, arsines,
In the presence of a catalyst comprising an external strong electron donor selected from the group of strong electron donors consisting of phosphoramides and alcoholates, 35-90 mol% ethylene and 1
0-65 mol% propylene is reacted, whereby
The amount of polypropylene in the second reactor during the reaction is 65
Sufficient to produce impact polypropylene containing ~ 99 wt% polypropylene and 1-35 wt% ethylene / propylene rubber, said polypropylene being selected from polypropylene homopolymer and random copolymer containing up to 5 wt% comonomer. A method for producing impact polypropylene, comprising the step of producing impact polypropylene. 19. A gas phase fluidized bed reactor used to produce impact polypropylene is provided under the following conditions: temperature 45-9.
0 ° C., pressure 200 to 550 psi (1,378 to 3,7
90 kPa), hydrogen / propylene molar ratio 0.0015-
0.40, ethylene / propylene molar ratio 0.45-2.
5, titanium concentration 0.13 to 2.16 wt% (based on the total catalyst slurry), organoaluminum compound / silicon compound molar ratio 1 to 150, organoaluminum compound / titanium molar ratio 25 to 300, and organoaluminum compound / external The production method according to claim 18, which is operated at a strong electron donor molar ratio of 0.5 to 100. 20. 50-65 mol% ethylene and 35
The production method according to claim 18, wherein -50 mol% is reacted. 21. The amount of propylene present during the reaction is
The production method according to claim 18, which is 30 to 60 mol% of the total gas. 22. The polypropylene present in the reaction is
Under the following conditions: temperature 45 to 95 ° C, pressure 250 to 700
psi (1,723-4,823 kPa), hydrogen / propylene molar ratio 0.001-0.2, titanium concentration 0.13
~ 2.16 wt% (based on total catalyst slurry), organoaluminum compound / silicon compound molar ratio 1-150,
And organoaluminum compound / titanium molar ratio 25 to 3
19. The process according to claim 18, wherein the catalyst and polypropylene are prepared at 00 and sent from the first reactor to the second reactor, which is an impact polypropylene reactor. 23. The reaction product of the solid catalyst component (A) comprises 60 to 85% by weight of magnesium chloride and 5 to 15 of titanium tetrachloride.
The production method according to claim 18, wherein the reaction is performed in an amount that produces a weight ratio of 10 to 25% by weight and an internal strong electron donor. 24. The reaction product of the solid catalyst component (A) is prepared by using 68 to 77% by weight of magnesium chloride and 8 to 12 of titanium tetrachloride.
24. The process according to claim 23, wherein the reaction is performed in an amount that produces a weight percentage of 15 to 20 wt% of the internal strong electron donor. 25. The catalyst according to claim 18, wherein the catalyst has an organoaluminum compound / silicon compound molar ratio of 5 to 25, an organoaluminum compound / titanium molar ratio of 50 to 100, and an organoaluminum compound / externally charged donor molar ratio of 1 to 10. The manufacturing method described. 26. The internal strong electron donor of (a) is diethylene phthalate, the silicon compound of (B) is cyclohexylmethyldimethoxysilane, the organoaluminum compound of (C) is totiethylaluminum, and the external strong electron of (D). The method according to claim 18, wherein the donor is p-ethoxyethyl benzoate. 27. (I) Melt flow rate 0.5 to 20 g / 10
65-99% by weight containing at least 95% by weight propylene having a content and a xylene dissolution content of 1-6% by weight
Polypropylene and (II) 35-90 mol% ethylene and 1-35 wt% containing 10-65 mol% propylene with a unique microstructure present in less than 22% in the PEP configuration as determined by C-13 NMR.
Of an ethylene / propylene copolymer rubber according to claim 1, wherein the impact polypropylene composition comprises a fully polymerized blend of at least 12 Gardner impact strengths per weight percent rubber ratio when the amount of rubber is less than 15 weight percent. Impact polypropylene composition having an overall melt flow rate of 30-60 g / 10 minutes after peroxide decomposition. 28. The polypropylene of (I) has a melt flow rate of 1-10 g / 10 min and a xylene dissolution content of 1.2-.
28. The composition of claim 27 having 4.5% by weight. 29. The composition of claim 27, wherein the ethylene / propylene copolymer rubber of (II) has a unique microstructure present in less than 20% in the PEP composition. 30. When the amount of rubber is less than 15% by weight, the composition has a Gardner impact strength to weight% rubber ratio of at least 15 and, after peroxide decomposition, 30 to 30%.
28. The composition of claim 27 having an overall melt flow rate of 45 g / 10 minutes. 31. (I) Melt flow rate 0.5 to 20 g / 10
65-99% by weight containing at least 95% by weight propylene having a content and a xylene dissolution content of 1-6% by weight
Polypropylene and (II) 35-90 mol% ethylene and 1-35 wt% containing 10-65 mol% propylene with a unique microstructure present in less than 22% in the PEP configuration as determined by C-13 NMR.
Of an ethylene / propylene copolymer rubber according to claim 1, wherein the rubber in the composition comprises at least 5% particle shape having a cross-sectional area of at least 0.4 μm ^2. An impact polypropylene composition. 32. The rubber in the composition is 0.4 to ¹ μm ^2.
32. The composition of claim 31, which is at least 5% particle shape having a cross-sectional area between. 33. The composition of claim 31, wherein at least 8% of the particles have a cross-sectional area of at least 0.4-1 μm ² . 34. Titanium tetrachloride is reacted with polypropylene and (A) (a) a magnesium compound suspended in the presence of an organic acid chloride in an organic solvent under vapor phase fluidized bed reactor conditions. To produce a solid material containing an internal strong electron donor that is generated in situ, and the magnesium compound is represented by the following formula: MgQ _2-n X _n (wherein each Q is independently , An alkoxide, an aryl oxide, or a carboxylate group, X
Is halogen and n is 0 or 1. ), (B) decanting, and then washing the solid substance with an organic solvent that does not dissolve the solid substance, (c) contacting the suspended solid substance with titanium tetrachloride in the organic solvent. And (d) decanting and then washing the solid material with an organic solvent that does not dissolve the solid material; (B) general formula: SiR _m (OR ′) _{4 − m} (wherein R is selected from an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, R ′ is an alkyl group, and m is 0 or an integer of 1 to 3,
When m is 2 or 3, a plurality of R groups may be the same or different, or when m is 0, 1 or 2, a plurality of R'groups may be the same or different,
And / or when R is an alkyl group, R ′ is R
A silicon compound which is the same as or different from R); (C) General formula: R ″ _n AlX _3-n (wherein R ″ is an alkyl group and X is A halogen or hydrogen atom, and n is an integer of 1 to 3, and when n is 2 or 3, a plurality of R ″ groups may be the same or different) Compounds: (D) ethers, esters, ketones, phenols, amines, amides, imines, nitriles, phosphines, phosphites, stibines, arsines,
In the presence of a catalyst comprising an external strong electron donor selected from the group of strong electron donors consisting of phosphoramides and alcoholates, 35-90 mol% ethylene and 1
0-65 mol% propylene is reacted and the amount of polypropylene in the reaction is sufficient to produce an impact copolymer containing 65-99 wt% polypropylene and 1-35 wt% ethylene / propylene rubber. , The polypropylene is selected from polypropylene homopolymers and random copolymers containing up to 5% by weight of comonomers, and the organoaluminum compound / external strong electron donor molar ratio is raised or lowered between 0.5 and 100. Proportionately increasing or decreasing the rubber concentration in the impact polypropylene between 1 and 35, produced at constant residence time, temperature and gas composition during the production of impact polypropylene. How to control the amount of rubber. 35. The method of claim 34, wherein the organoaluminum / external strong electron donor molar ratio is raised or lowered between 1 and 5 to reduce or increase rubber yield. 36. The method of claim 34, wherein the organoaluminum / external strong electron donor molar ratio is raised or lowered by injecting the desired amount of strong electron donor into the carrier.