High melt flow rate, impact-resistant propylene copolymer and method for production thereof

FIELD: chemistry.

SUBSTANCE: polymerisation method involves contacting propylene and optionally at least one other olefin with a catalyst composition in a first polymerisation reactor under gas-phase polymerisation conditions, the catalyst composition containing a procatalyst, a cocatalyst and a mixed external electron donor (M-EED) containing a first selectivity control agent (SCA1), a second selectivity control agent (SCA2), and an activity limiting agent (ALA); forming, in a first polymerisation reactor, an active propylene-based polymer having a melt flow rate greater than about 100 g/10 min as measured in accordance with ASTM D1238-01 (230°C, 2.16 kg); contacting the active propylene-based polymer with at least one olefin in a second reactor under polymerisation conditions; and obtaining an impact-resistant propylene copolymer having a melt flow rate greater than about 60 g/10 min. A version of the method and the polymer is disclosed.

EFFECT: obtaining an impact-resistant polymer with a high melt flow rate and low content of volatile substances.

10 cl, 4 tbl, 8 ex

Priority requirement

This application is application - partial continuation of International patent application number PCT/US2008/073882, filed August 21, 2008, which claims the priority of provisional patent application U.S. No. 60/957888, filed August 24, 2004, the complete contents of which is introduced herein by reference.

Background of invention

The demand for high-impact copolymers based on propylene with high speed melt flow continues to grow, as continued growth in consumption of more modern polymers. Core propylene impact copolymers are copolymers obtained by polymerization, and do not include, for example, light cracking. It is very difficult to obtain a propylene impact copolymers with a high turnover of direct melt polymerization. Conventional polymerization catalysts usually require the use of very high concentrations of hydrogen for the formation of the polymer phase matrix with the fluidity of the melt above the fluidity of the melt end propylene impact copolymer. In many cases, the provision of high hydrogen concentration is impossible due to the limitations of performance of reactor security requirements and/or economic considerations.

It is desirable way p is liberizatsii to obtain a propylene impact copolymer with high fluidity of the melt. More desirable is a method of obtaining a propylene impact copolymer with high fluidity of the melt and high toughness. Also desirable is a method of obtaining a propylene impact copolymer with high fluidity of the melt and high toughness low risk, or no risk of infringement of process.

Summary of the invention

The present invention relates to a polymerization process for the production of propylene impact copolymer with a high melt flow index. Propylene impact copolymer with a high melt flow index may also have high impact strength. The methods of the present invention are the core ways and do not include light cracking.

In the embodiment, the invention relates to a method of polymerization. The polymerization method includes a gas-phase polymerization or the receipt by gas-phase polymerization active polymer based on propylene in the first polymerization reactor. Active polymer based on polypropylene has a melt flow index more than about 100 g/10 min, measured according to ASTM D1238-01 (230°C, 2,16 kg). The method includes the introduction of active polymer based on propylene in the second curing PE is ctor. In the second reactor polymer based on propylene in contact with at least one olefin in the polymerization conditions. The method further includes obtaining a propylene impact copolymer having a melt flow index more than approximately 60 g/min

In the embodiment of the invention the method includes maintaining the molar ratio of N₂/S₃less than 0.3 in one or both reactors.

In the embodiment of the invention the method includes obtaining a propylene impact copolymer having a content of volatile compounds, less than about 65 μg/g, the Content of volatile compounds measured in accordance with standard VW PV3341.

The present invention relates to another method. In the embodiment, the invention relates to a method of polymerization which comprises effecting contact of at least one olefin with an active polymer based on propylene in a polymerization reactor under the conditions of polymerization. Active polymer based on polypropylene has a melt flow index more than about 100 g/10 min Method further includes obtaining a propylene impact copolymer having a melt flow index more than about 85 g/10 minutes

In the embodiment, the invention polymerization the reactor is the reactor polymerization in the gas phase.

In the embodiment of the invention the method comprises maintaining the ratio of N₂/S₃in the reactor is less than 0,20.

In the embodiment of the invention the method includes obtaining a propylene impact copolymer having a content of volatile compounds, less than about 65 μg/g

The present invention relates to the composition. In the embodiment, the invention relates to propylene to the impact resistant copolymer which comprises a polymer based on propylene having a melt flow index more than about 100 g/10 min, and a copolymer of propylene/ethylene, dispersed in a polymer based on propylene. Propylene impact copolymer has a value of Fc from about 5 wt.% to about 50 wt.% and the Ec value from about 20 wt.% to about 90 wt.%. Propylene impact copolymer has a melt flow index more than about 60 g/10 minutes

The advantage of the present invention is to improve the method of producing propylene impact copolymer and, in particular, to obtain a propylene impact copolymer with a high melt flow index.

The advantage of the present invention is to provide an improved propylene impact copolymer.

Freemusicdownloads copolymer is to provide Nekrestyanov propylene impact copolymer, having a high melt flow index.

Detailed description of the invention

In the embodiment, the invention relates to a method of polymerization. The polymerization method includes a gas-phase polymerization (or the receipt by the polymerization in the gas phase) active-based polymer of propylene having a melt flow index (MFR) greater than about 100 g/10 min MFR is measured in accordance with ASTM D1238-01 (230°C, 2,16 kg). Active polymer based on propylene is formed in the first polymerization reactor under the conditions of polymerization (i.e. polymerization in the gas phase). The method further includes the introduction of active polymer based on propylene in the second polymerization reactor, where the active polymer based on propylene in contact with at least one olefin other than propylene, in the conditions of polymerization. The method further includes obtaining a propylene impact copolymer having a melt flow index more than about 60 g/10 minutes

As used herein, "active polymer" is a polymer containing such quantity of active catalyst (usually immersed in it), which is able to provide additional polymerization when exposed to olefin conditions of polymerization. In the embodiment, and is gaining active catalyst, immersed in active polymer based on propylene, is self-limiting catalytic composition, which includes precatalytic composition, socialization and a mixed external electron donor (M-EED). M-EED includes first agent selective regulation (SCA1), a second selective agent regulation (SCA2) and the agent that limits activity (ALA). It should be understood that the M-EED may include three or more SCA and/or two or more ALA.

Precatalytic composition in the composition of this catalyst may be precatalytic composition Ziegler-Natta. In the present catalytic compositions can be used any traditional pronatalist Ziegler-Natta. In the embodiment of the invention the composition of pronatalistic Ziegler-Natta contains the compound of the transition metal and the metal connection 2 groups. The transition metal compound may be a solid complex formed by the connection of the transition metal, for example, Hydrocarbonated, hydrocarbide, the halides of titanium, zirconium, chromium or vanadium, or mixtures thereof.

The transition metal compound has the General formula TrX_xwhere Tr is a transition metal, X represents halogen or_1-10hydrocarbonbearing or hydrocarbonous group, and x represents the number of data X groups in the compound in combination : the AI with a compound of the metal of group 2. Tr may be a metal of group 4, 5 or 6. In the embodiment of the invention, Tr represents a metal of group 4, such as titanium. X may be chloride, bromide,_1-4the alkoxide or phenoxide or mixtures thereof. In the embodiment of the invention X is chloride.

Non-limiting of the scope of the invention examples of suitable transition metal compounds that can be used to obtain precatalytic composition Ziegler-Natta are TiCl₄, ZrCl₄, HfCl₄, TiBr₄, TiCl₃, Ti(OC₂H₅)₃Cl, Zr(OC₂H₅)₃Cl, Ti(OC₂H₅)Br, Ti(OC₃H₇)₂Cl₂, Ti(OC₆H₅)₂Cl₂, Zr(OC₂H₅)₂Cl₂and Ti(OC₂H₅)Cl₃. Can also be used a mixture of compounds of data transition metals. No restrictions on the number of transition metal compounds is not imposed, because at least there is one connection of the transition metal. In the embodiment of the invention the transition metal compound is a compound of titanium.

Non-limiting volume of claims examples of suitable compounds of group 2 metal include magnesium halides, dialkoxy, halides alkoxyamine, oxychloride magnesium, dialkylamino, magnesium oxide, magnesium hydroxide and Carbo who silty magnesium. In the embodiment of the invention the compound of group 2 metal is magnesium dichloride.

In the embodiment of the invention the composition of pronatalistic Ziegler-Natta is a mixture of titanium compounds supported on magnesium compound or otherwise obtained from compounds of magnesium. Suitable magnesium compounds include anhydrous magnesium chloride, adducts of magnesium chloride, dialkoxy or aryloxy magnesium or karboksilirovanie dialkoxy or aryloxy magnesium. In the embodiment of the invention the magnesium compound is di(C_1-4)a magnesium alkoxide, such as dioxirane.

Non-limiting volume of claims examples of suitable titanium compounds include titanium alkoxides, aryloxides titanium and/or titanium halides. Compounds used to produce the compositions of pronatalistic Ziegler-Natta include one or more di(C_1-4)alkoxides of magnesium, dihalogenide magnesium, alkoxylated magnesium or mixtures thereof and one or more Tetra(C_1-4)alkoxides of titanium, tetrachloride titanium, (C_1-4)alkoxylation titanium or mixtures thereof.

The composition of the precursor can be used to produce compositions of pronatalistic Ziegler-Natta, which is well known in this field. The composition of the precursor can be obtained by chlorination prior is sustained fashion mixed compounds of magnesium, the titanium compounds or mixtures thereof and may include the use of one or more compounds called "limiting agents, which promote the education or solubilize certain compositions according to the mechanism of the exchange reaction, the solid/solid. Non-limiting volume of claims, limiting examples of suitable agents include trialkylborane, especially triethylborane, phenolic compounds, especially cresol, and silanes.

In the embodiment of the invention the composition of the precursor is mixed compound of magnesium/titanium formula Mg_dTi(OR_e)_fX_gwhere R_erepresents an aliphatic or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms or COR'where R' is an aliphatic or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms; each OR₃the group is the same or different; X independently represents a chlorine, bromine or iodine; d is equal to the value of from 0.5 to 56, or from 2 to 4 or 3; f is 2-116 or 5-15; or g is 0.5-116 or 1-3 or 2. The precursor can be obtained by controlled precipitation of removing alcohol from the reaction mixture used in the preparation. In the embodiment of the invention, the reaction medium comprises a mixture of aromatic liquids, especially chlorinated arene is political connections, such as chlorobenzene, alkanols, especially ethanol, and inorganic gloriouse agent. Suitable inorganic gloriouse agents include chlorinated silicon, aluminum and titanium, such as titanium tetrachloride or trichloride titanium, in particular titanium tetrachloride. Gloriouse agents cause partial chlorination, which leads to the formation of a precursor containing a relatively high level alkoxyamine(s). Removing alcohol from the solution used in the chlorination leads to the precipitation of the solid precursor having the desired morphology and specific surface area. The precursor is separated from the reaction medium. In addition, the obtained precursor is a particularly uniform in particle size and has a resistance to crushing and destruction of the formed pronatalistic. In the embodiment of the invention the composition of the precursor is Mg₃Ti(OEt)₈Cl₂.

The precursor is then converted into solid precatalysts by additional interaction (halogenation) with an inorganic compound of a halogen, preferably halogen-containing compound of titanium, and the introduction of an internal electron donor. If you do not enter the internal electron donor in the predecessor in sufficient quantities, it mo is et to be added separately before, during or after halogenation. This procedure may be repeated one or more times, optionally in the presence of additional additives or auxiliaries, and the final solid product is washed with an aliphatic solvent. For use in this invention any suitable method of obtaining, retrieving and storing of solid pronatalistic.

One of the suitable methods of halogenation predecessor is the interaction of the precursor at an elevated temperature with a halide of tetravalent titanium, optionally in the presence of a hydrocarbon or halogenated hydrocarbon diluent. The preferred halide of tetravalent titanium is titanium tetrachloride. Optional hydrocarbon or halogenated hydrocarbon solvent used in the preparation of pronatalistic olefin polymerization, preferably contains up to 12 carbon atoms, inclusive, or up to 9 carbon atoms, inclusive. Examples of hydrocarbons include pentane, octane, benzene, toluene, xylene, alkyl benzenes and decahydronaphthalene. Examples of aliphatic halogenated hydrocarbons include methylene chloride, metropolit, chloroform, carbon tetrachloride, 1,2-dibromoethane, 1,1,2-trichloroethane, tricorcelexa, dichloromethan and tetrol rattan. Examples of halogenated aromatic hydrocarbons include chlorobenzene, Brabanthal, dichlorbenzene and chlorotoluene. Aliphatic halogenated hydrocarbon may be a compound containing at least two chlorine-containing substituent, such as carbon tetrachloride or 1,1,2-trichloroethane. Aromatic halogenated hydrocarbon may be chlorobenzene or o-chlorotoluene.

Halogenoalkane can be repeated one or more times, optionally followed by washing with an inert liquid such as an aliphatic or aromatic hydrocarbon or halogenated hydrocarbon, between processes of halogenation and subsequent halogenation. To remove labile compounds, especially TiCl₄can be used additionally, optionally, one or more extraction processes, including the implementation of contact with the inert liquid solvent, especially an aliphatic or aromatic hydrocarbon or an aliphatic or aromatic halogenated hydrocarbons, especially at elevated temperatures above 100°C or greater than 110°C.

In the embodiment of the invention the composition of pronatalistic Ziegler-Natta includes a solid catalytic component obtained by (i) suspendirovanie dialkoxybenzene in aromatic hydrocarbon or halogenic the bath hydrocarbon, which is liquid at normal temperatures, (ii) implementation of contact dialkoxybenzene with the titanium halide, and then (iii) implementation of contact of the resulting composition a second time with the titanium halide, and implementation of contact dialkoxybenzene with complex fluids aromatic dicarboxylic acid at some point during the processing of the titanium halide in (ii).

In the embodiment of the invention the composition of pronatalistic Ziegler-Natta includes a solid catalytic component obtained by (i) suspendirovanie material precursor of the formula Mg₄Ti(OR_e)_fX_g(as discussed above) in an aromatic hydrocarbon or halogenated hydrocarbon, which is liquid at normal temperatures, (ii) implementation of contact of the precursor with a titanium halide and then (iii) implementation of contact of the resulting composition a second time with the titanium halide, and implementation of contact of the precursor complex fluids aromatic dicarboxylic acid at some point during the processing of the titanium halide at stage (ii).

The composition of pronatalistic includes an internal electron donor. As used herein, "internal electron donor" is a compound added to or otherwise obtained in the course of education compositeoperator, which donates a pair of electrons to one or more metals contained in the resulting composition pronatalistic. Making no commitment to any particular theory, the inventors believe that the internal electron donor contributes to the regulation of the formation of active centers which enhance the stereoselectivity of the catalyst.

In the embodiment of the invention, the internal electron donor is a dual connection. "Dual compound", as used herein, is a compound containing at least two oxygen-containing functional groups, oxygen-containing functional groups separated by at least one saturated With₂-C₁₀hydrocarbon chain, which may optionally contain heteroatom(s). Dual connection can be phthalate, simple fluids, succinate, phenylendiamin, maleate, malonate, glutarate, dialkoxybenzene, bis(alkoxyphenyl), complex diology ether complex keeeper, complex alkoxyalkyl ether, bis(alkoxyalkyl)fluoran and any combination thereof.

In the embodiment of the invention the internal electron donor is diisobutylphthalate and/or di-n-butylphthalate.

In the embodiment of the invention, the internal electron donor is 9,9-bis(methoxymethyl)-N-fluoren.

In the var the ante embodiment of the invention, the internal electron donor is phenylendiamin.

The composition of pronatalistic Ziegler-Natta may also include inert material media. The carrier may be an inert solid substance which does not have a negative impact on the catalytic activity of transition metal compounds. Examples include metal oxides, such as alumina, and oxides of nonmetals such as silicon dioxide.

The catalytic composition of the present invention includes socialization. Socialization for use with the above composition pronatalistic Ziegler-Natta can be a composition comprising aluminum. Non-limiting volume of claims examples of suitable aluminium-containing compositions include alyuminiiorganicheskikh compounds such as trialkylaluminium, dialkylaminomethyl, alkylamineacetate, dialkylaminoalkyl, alkylhalogenide, dialkylaminoalkyl and alkylamidoamines compounds containing 1-10, or 1-6 carbon atoms in each alkyl or alkoxide group. In the embodiment, the invention socialization is a C_1-4trialkylaluminium connection, such as triethylaluminium (tea or TEAl). The molar ratio of aluminum to titanium is 10-200:1 or 35 to 50:1. In the embodiment of the invention the molar ratio of aluminum to titanium is 45:1.

Catalic the ical composition of the present invention includes a mixed external electron donor (M-EED), which includes the first agent selective regulation (SCA1), a second selective agent regulation (SCA2) and the agent that limits activity (ALA). As used in the present invention, "the external electron donor (or EED) is a compound added regardless of education pronatalistic, which contains at least one functional group which is able to give a pair of electrons to the metal atom. Making no commitment to any particular theory, the inventors believe that the use of one or more external electron donor in the catalytic composition affects the following properties of the resulting polymer: the level of tact (i.e. soluble in xylene material), molecular weight (i.e., the melt flow index), molecular weight distribution (MWD), the melting point and/or the content of the oligomer.

Non-limiting volume of claims examples of suitable compounds for SCA include silicon compounds such as alkoxysilane; ethers and polyethers, such as alkalemia, cycloalkyl, arrouye, mixed alkalemia/akrilovye, mixed alkalemia/cycloalkane and/or mixed cycloalkane/akrilovye ethers, and/or polyethers; esters and polyesters, especially alkalemia, cycloalkyl and/and and arrowie esters of monocarboxylic or dicarboxylic acids, such as aromatic monocarboxylic or dicarboxylic acid, alkalemia or cycloalkyl ethers, or derivatives of simple thioethers data esters or polyesters, such as alkalemia simple ester derivatives complex alilovic esters or complex diesters of aromatic monocarboxylic or dicarboxylic acids, and substituted by heteroatoms 15-th and 16-th group all derivatives of the aforementioned compounds; and amine compounds such as cyclic, aliphatic or aromatic amines, especially paralowie or pyridine compounds, above all SCA containing only 2 to 60 carbon atoms and from 1 to 20 carbon atoms in any alkyl or alkalinous group, from 3 to 20 carbon atoms in any cycloalkyl or cycloalkanones group and from 6 to 20 carbon atoms in any aryl or Allenova group.

In the embodiment of the invention SCA1 and/or SCA2 is silane composition having the General formula (1):

SiR_m(OR')_4-m,

where R is independently in each case represents a hydrogen atom or hydrocarbonous or amino group, optionally substituted by one or more substituents containing one or more heteroatoms of groups 14, 15, 16 or 17. R contains up to 20 atoms, not counting hydrogen atoms and halogen, R' represents a C_1-20alkyl g is the SCP, and m is 0, 1 or 2. In the embodiment of the invention R represents a C_6-12aryl, alkyl or aralkyl,_3-12cycloalkyl,_3-12branched alkyl or C_3-12the cyclic amino group, R' represents a C_1-4alkyl, and m is 1 or 2.

In the embodiment of the invention SCA1 is dimethoxysilane. Dimethoxysilane may contain at least one secondary alkyl and/or one secondary amino group directly bonded to the silicon atom. Non-limiting volume of claims examples of suitable dimethoxysilane include dicyclopentadienyliron, methylcyclohexylamine, diisobutyldimethoxysilane, isopropylidenedicyclohexanol, diisobutyldimethoxysilane, tert-utilizationfocused, cyclopentadienylmagnesium, bis(pyrrolidino)dimethoxysilane, bis(perhydrosqualene)dimethoxysilane and any combination of the above compounds.

In the embodiment of the invention SCA1 is a composition for increased stiffness. "Composition for increased stiffness"as used herein, is a composition that, when working according to the process conditions of the present invention, increases, or otherwise enhances the rigidity of the resulting polymer in the polymerization conditions. Not greiciausia examples of suitable amplifiers stiffness include any of dimethoxysilane, above.

In the embodiment of the invention SCA1 is dicyclopentadienyliron.

In the embodiment of the invention SCA2 is a compound of silicon selected from diethoxyethane, triethoxysilane, tetraethoxysilane, triethoxysilane, dimethoxysilane containing two linear alkyl groups, dimethoxysilane containing two alkeneamine group, simple diapir, dialkoxybenzene and any combination.

Non-limiting examples of suitable silicon compounds for SCA2 include dimethyldiethoxysilane, wikimediamessages, n-octylpyrimidine, n-octadecyltrimethoxysilane, metildigoxin, 3-chloropropionitrile, 2-chloroethylthiomethyl, allylimidazole, (3,3,3-cryptochromes)metaldimension, n-propylmethyldimethoxysilane, chlorodimethylvinylsilane, di-n-octylimidazolium, vinyl(chloromethyl)dimethoxysilane, methylcyclohexanecarboxylic, vinylpyridinium, 1-(triethoxysilyl)-2-(diethoxymethylsilane)ethane, n-altimetrical, octatonic-1,3,5-trisilane, n-octadecyltriethoxysilane, methacryloxypropyltrimethoxysilane, 2-hydroxy-4-(3-methyldeoxycytidine)diphenylmethane, (3-glycidoxypropyl)metildigoxin, dodecyltriethoxysilane, dimethyldiethoxysilane, diethyldichlorosilane, ,1 diethoxy-1-silacyclopentane-3-ene, chlorodimethylvinylsilane, bis(methyldeoxycytidine)amine, 3-aminopropyltriethoxysilane, (methacryloxyethyl)metildigoxin, 1,2-bis(metaldetection)ethane and diisobutyldimethoxysilane, VINYLTRIMETHOXYSILANE, vinyltriethoxysilane, benzyltriethylammonium, butyltrichlorosilane, (triethoxysilyl)cyclohexane, O-(vinyloxyethyl)-N-triethoxysilylpropyl, 10-undecanoylimidazoline, n-(3-triethoxysilylpropyl)pyrrole, N-[5-(trimethoxysilyl)-2-Aza-1-oxobutyl]caprolactam, (3,3,3-cryptochromes)trimethoxysilane, triethoxysilane ethylenglykolether, (S)-N-triethoxysilylpropyl-O-Methocarbamol, triethoxysilylpropyl, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, (3-triethoxysilylpropyl)-tert-BUTYLCARBAMATE, steriletechnologies, 2-(4-pyridylethyl)triethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, (S)-N-1-phenylethyl-N'-triethoxysilylpropyl, (R)-N-1-phenylethyl-N-triethoxysilylpropyl, N-phenylaminopyrimidine, N-phenylaminopyrimidine, phenethyltrimethoxysilane, intercritical, n-octyltrimethoxysilane, n-octyltriethoxysilane, 7-activitiesaccessible, S(octanoyl)mercaptopropionate, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, N-methylaminopropane isilon, 3-methoxypropionitrile, methacryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane and O-(methacryloxyethyl)-N-(triethoxysilylpropyl)carbamate, tetramethoxysilane and/or tetraethoxysilane.

In the embodiment of the invention SCA2 may be methylcyclohexanecarboxylic, di-isobutyltrimethoxysilane, n-propyltriethoxysilane, tetraethoxysilane, di-n-butyldimethylsilyl, benzyltriethylammonium, but-3-initialisieren, 1-(triethoxysilyl)-2-penten, (triethoxysilyl)cyclohexane, and any combination of the above-mentioned compounds.

In the embodiment of the invention SCA2 selected from dimethoxysilane containing two linear alkyl groups, dimethoxysilane containing two alkeneamine group or a hydrogen atom, where one or more hydrogen atoms may be substituted with halogen, and any combination.

In the embodiment of the invention SCA2 can be simple fluids, the dimer simple diapir, dialkoxybenzene, a dimer of dialkoxybenzene, dialkoxybenzene connected linear hydrocarbon group, and any combination. It should be noted that simple diesters for ALA, above, is applicable as a non-limiting amount of claims examples for simple diapir SCA2.

In the embodiment, and is gaining SCA2 is a composition for improving the melt flow index. "Composition that improves the melt flow index", as used herein, is a composition that, for the process of the present invention, increases the melt flow index of the resulting polymer in the conditions of this polymerization process. Composition, increasing the melt flow index can be any silane composition suitable for SCA2, as disclosed herein, simple fluids, alkoxybenzyl, ester, ketone, amide and/or amine.

M-EED includes an agent that limits activity (ALA). "Agent, limiting activity", as used herein, is a material that reduces the catalytic activity at elevated temperatures, namely, in a polymerization reactor under the conditions of polymerization at a temperature above about 100°C. the Use of ALA results in self-limiting catalytic composition. As used herein, "self-limiting" catalytic composition is a catalytic composition, which shows reduced activity at a temperature of more than approximately 100°C. in Other words, "self-limiting" means the decline of catalytic activity when the reaction temperature increases Wyse°C, compared with the catalytic activity in normal conditions of polymerization when the reaction temperature is usually below 80°C. in Addition, as a practical standard, if the polymerization process, such as in a fluidized bed, gas-phase polymerization occurring under normal conditions, the process can stop and the destruction layer the result is reduced risk of agglomeration of the polymer particles, it is said catalytic composition is "self-limiting".

As standard measures polymerization activity at elevated temperatures used in this document, the catalyst activity was regulated so as to compensate for different concentrations of monomer due to temperature. For example, if you are using liquid-phase conditions (suspension or solution) polymerization, introduced a correction factor to the reduced solubility of propylene in the reaction mixture at elevated temperatures. That is, the catalytic activity "normalize"to compensate for the reduced solubility compared to the lower temperature, especially standard 67°C. the "Normalized" activity at the temperature T, or a_T, is defined as the measured activity (or the weight of the polymer/weight of catalyst/hour) when the temperature is ur T, multiplied by a correction factor for concentration, [P(67)]/ [P(T)], where [P(67)] represents the concentration of propylene at 67°C and [P(T)] represents the concentration of propylene at a temperature T. the Equation for calculating a normalized activity is presented below.

Normalized activity (A)=[P(67)]/[P(T)]×Activity (T)

In equation activity when the temperature T is multiplied by the ratio of the concentration of propylene at 67°C, the concentration of propylene at a temperature So Obtained normalized activity (A), adjusted to reduce the concentration of propylene with increasing temperature, can be used for comparison of catalytic activities in various temperature conditions. Correction factors are listed below for terms used in liquid-phase polymerization.

The correction factor assumes that the polymerization activity of uvelichivaet is linear with the concentration of propylene in the used conditions. The correction factor is a function of the used solvent or diluent. For example, the following correction factors are given for the conventional mixture With_6-10aliphatic hydrocarbon (Isopar™E, available from Exxon Chemical Company). In terms of gas-phase polymerization, the solubility of the monomer is usually not an indicator, and the activity is usually not correct for temperature differences. There is activity and normalized activity is the same.

"The ratio of the normalized activity" is defined as A_T/A₆₇where A_Trepresents the activity at a temperature T and A₆₇represents activity at 67°C. This value can be used as an indicator of changes in the activity depending on the temperature. For example, a₁₀₀/A₆₇0.30 , which shows that the activity of the catalyst at 100°C is only 30 percent of the catalyst activity at 67°C. it is Established that at 100°C. the ratio of A₁₀₀/A₆₇35% or less provides a catalytic system which is self-limiting system.

ALA can represent complex aromatic ester or its derivative, complex aliphatic ester or its derivative, simple fluids, complex poly(alkalophilicity) ether, and combinations thereof. Non-limiting volume of approx claims the market suitable aromatic esters include complex _1-10alkalemia or cycloalkyl esters of aromatic monocarboxylic acids. Suitable substituted derivatives of them include compounds substituted on both aromatic rings or ester group one or more substituents containing one or more heteroatoms of groups 14, 15 or 16, especially oxygen. The examples of these substituents include groups simple (poly)Olkiluoto ether, simple cycloalkyl ether, simple kilowog ether, simple Arakelova ether, simple alkylthiophene, simple ALLtogether, dialkylamino, diarylamino, dialkylamino and trialkylsilanes. Complex aromatic ether carboxylic acids may be complicated With_1-20hydrocarbonyl ester benzoic acid, where gidrolabilna group is unsubstituted or substituted by one or more substituents containing heteroatoms of groups 14, 15 or 16, and its derivatives With simple_1-20(poly)hidrocarburos ether or_1-4alkylbenzoates and_1-4alkylated in the ring derivative, or methylbenzoate, ethylbenzoic, propylbenzoate, methyl-p-methoxybenzoate, methyl-p-ethoxybenzoate, ethyl-p-methoxybenzoate and ethyl-p-ethoxybenzoate. In the embodiment of the invention complex aromatic ether carboxylic acid is ethyl-n-ethoxybenzoate.

In the embodiment, and is gaining ALA is an aliphatic ether. Complex aliphatic ester may be an ester With₄-C₃₀aliphatic acids, can be complex mono - or poly- (two or more) ether, may be linear or branched, may be saturated or unsaturated, and any combination thereof. Ester With₄-C₃₀aliphatic acids may also be substituted by one or more substituents containing a heteroatom from group 14, 15 or 16. Non-limiting volume of claims examples of suitable ester-C₄-C₃₀aliphatic acid include complex_1-20alkalemia esters of aliphatic C_4-30monocarboxylic acids, complex_1-20alkalemia esters of aliphatic C_8-20monocarboxylic acids, With_1-4allyl mono - and diesters of aliphatic C_4-20monocarboxylic acids and dicarboxylic acids, complex_1-4alkalemia esters of aliphatic C_8-20monocarboxylic acids and dicarboxylic acids and C_4-20mono - or polycarboxylate derivatives With_2-100(poly)glycols or_2-100(poly)glycol ethers. In another embodiment of the invention complex air₄-C₃₀aliphatic acid may be isopropylmyristate and/or di-n-butylsilane.

In the embodiment of the invention ALA represents isopropylmyristate.

In a variant implementation of the ing the invention ALA is simple fluids. Simple fluids can be diakidoy simple fluids, represented by the following formula:

where R¹-R⁴represent independently from each other alkyl, aryl or aracelio group containing up to 20 carbon atoms, which optionally may contain a heteroatom from group 14, 15, 16 or 17, provided that R¹and R²can represent a hydrogen atom. Non-limiting volume of claims examples of suitable simple dialkylamino esters include simple dimethyl ether, simple diethyl ether, simple disutility ether, simple metaliteracy ether, simple methylbutanoyl ether, simple methylcyclohexylamine ether, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-di-n-butyl-1,3-dimethoxypropane, 2,2-Diisobutyl-1,3-dimethoxypropane, 2-ethyl-2-n-butyl-1,3-dimethoxypropane, 2-n-propyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-n-propyl-2-cyclohexyl-1,3-diethoxypropane and 9,9-bis(methoxymethyl)fluorene. In another embodiment, the invention is simple dialkylamino ester is 2,2-Diisobutyl-1,3-dimethoxypropane.

In the embodiment of the invention ALA represents a complex of poly(alkalophilicity) ether. Non-limiting volume of claims example is suitable complex of poly(alkalophilic) ethers include poly(allenglish)mono - or diacetate, poly(allenglish)mono - or demeritte, poly(allenglish)mono - or dilaurate, poly(allenglish)mono - or dioleate, glycerite(acetate), complex triglyceridemia broadcast With_2-40aliphatic carboxylic acids and any combination thereof. In the embodiment of the invention poly(alkylenglycol) a fragment of a complex of poly(alkylenglycol) ether is poly(ethylene glycol).

In the embodiment of the invention the molar ratio of aluminum to ALA may be 1,4-85:1 or 2.0-50:1 or 4-30:1. For ALA, which contains more than one carboxylate group, all of the carboxylate groups are effective components. For example, it is assumed that the molecule sebacina (cebacate), which contains two carboxylate functional groups, has two effective functional molecule.

In the embodiment of the invention, the catalytic composition comprises a molar ratio of Al to M-EED 0.5 to 25:1, or 1.0 to 20:1, or 1.5 to 15:1, or less than about 6.0, or less than about 5, or less than 4.5.

In the embodiment of the invention the molar ratio of Al:M-EED is 0.5 to 4.0:1. Not wanting to contact a specific theory, the inventors believe that the ratio Al/M-EED from 0.5:1 to 4.0:1 provides a sufficient amount of aluminum to maintain the polymerization reaction at normal temperatures of polymerization. Od is ako at elevated temperatures (due to the temperature variation or irregularity, for example) more aluminum fragments interact with other components of the catalyst. This leads to the disadvantage of aluminum, which slows down the reaction of polymerization. The downside of aluminum results in a corresponding decrease in the number of donor electrons, forming an integrated communication with aluminum. Free pair of electrons not associated complex relationships donors poison the catalytic system, which makes the reaction is self-extinguishing.

As used herein, "SCA" represents the combined amount (in moles) SCA1 and SCA2. In other words, only SCA=SCA1(mol)+SCA2(mol). The amount of ALA in the M-EED increases the capacity for self-restraint of the catalyst at elevated temperatures, while the number of SCA1 provides rigidity and SCA2 provides a melt flow index of the resulting polymer. The molar ratio of total SCA to ALA is 0.43-2,33:1 0.54-of 1.85:1 or of 0.67 to 1.5:1. The molar ratio of SCA1 to total SCA is 0,2-0,5:1, 0,25-0,45:1 or between 0.30 to 0.40:1. Applicants unexpectedly found that the regulation molar ratio of (1) to SCA1 SCA2 and/or (2) the total SCA to ALA and/or (3) SCA1 to total SCA gives a polymer with unique properties of high melt flow index and a high stiffness in combination with process flexibility self-limiting catalyst.

In the embodiment of the invention the molar assigned the e total SCA to ALA is 0.43-2,33:1, and the molar ratio SCA1 to total SCA is 0.2 to 0.5:1.

In the embodiment of the invention, the catalytic composition comprises a molar ratio of Al to the total SCA 1,4-85:1 or 2.0-50:1 or 4.0-30:1.

In the embodiment of the invention, the catalytic composition comprises a molar ratio of total SCA to ALA less than 1.0. Unexpectedly, the inventors have found that maintaining the molar ratio of the total SCA to ALA at the level of less than 1.0 significantly improves process flexibility process.

In the embodiment of the invention M-EED includes dicyclopentadienyliron (SCA1), a composition that increases the melt flow index (SCA2), and isopropylmyristate (ALA). In another embodiment of the invention SCA2 choose from methylcyclohexanecarboxylic, diisobutyldimethoxysilane, di-n-butyldiethanolamine, n-propyltriethoxysilane, benzyltriethylammonium, butyltrichlorosilane, (triethoxysilyl)cyclohexane, tetraethoxysilane, 1 ethoxy-2-(6-(2-ethoxyphenoxy)hexyloxy)benzene, 1-ethoxy-2-n-phenoxybenzoyl and any combination thereof.

The molar ratio between the various components of the present catalyst compositions are presented below in table 1.

This catalytic composition may comprise two or more embodiments of the invention, rusk is itih in this document.

In the embodiment of the invention the formation of the active polymer based on propylene is in the process of gas-phase polymerization, in which the catalytic composition is in contact with propylene and optionally one or more olefins in the first polymerization reactor. One or more olefinic monomers may be optionally introduced into the first polymerization reactor along with propylene to interact with the catalyst and the formation of polymer, copolymer (or fluidised bed of polymer particles). Non-limiting volume of claims examples of suitable olefin monomers include ethylene, With_4-20α-olefins such as 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 1-hepten, 1-octene, 1-mission 1-dodecen etc.;With_4-20diolefin, such as 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB) and Dicyclopentadiene; C_8-40vinyl aromatic compounds including styrene, o-, m - and p-methylsterol, divinylbenzene, vinylbiphenyl, vinylnaphthalene; and halogen-substituted C_8-40vinyl aromatic compounds, such as chloresterol and forstera.

As used herein, "polymerization conditions" are the parameters of temperature and pressure inside the polymerization reactor suitable for acceleration of polymerizate is between the catalytic composition and the olefin with the formation of the desired polymer. The polymerization process may be a gas-phase, slurry, or by polymerization in mass, flowing in one or more polymerization reactors. Accordingly, the polymerization reactor may be a gas-phase polymerization reactor, liquid-phase polymerization reactor, or a combination.

It is clear that the presence of hydrogen in the polymerization reactor is one of the conditions of polymerization. During the polymerization, hydrogen is the agent of the transfer circuit and affects the molecular weight (and therefore, the melt flow index) of the resulting polymer.

In the embodiment of the invention, the polymerization proceeds as a polymerization in the gas phase. As used herein, "polymerization in the gas phase or gas-phase polymerization" is the passage of the ascending environment of fluidization, the environment of fluidization, containing one or more monomers in the presence of a catalyst through a fluidized bed of polymer particles is maintained in the fluidized state of the environment of fluidization. "Fluidization", "fluid" or "pseudoviruses" represents the implementation of the contact gas-liquid, in which a layer of finely ground polymer particles are lifted and agitated by a rising stream of gas. Pseudois the tion occurs in the layer of particles, when the upward flow of fluid through the voids of the layer of particles reaches differential pressure, and the increment of the resistance of friction is greater than the mass of particles. Thus, the "fluidized bed" represents the set of polymer particles suspended in the fluidized state by the flow pseudoviruses environment. "Pseudoviruses environment" is one or more gaseous olefins, and optionally a carrier gas (such as H₂or N₂and optional liquid (such as hydrocarbons), which rises through the gas-phase reactor.

Typical gas-phase polymerization reactor (or reactor polymerization in the gas phase) includes the capacity (i.e., the reactor), fluidized bed, the distribution plate, inlet and outlet pipes, compressor, circulating gas cooler or heat exchanger and the discharge system of the product. The container includes a reaction zone and a zone speed reduction, each of which is located above the distribution plate. The layer is located in the reaction zone. In the embodiment of the invention pseudozyma environment includes gaseous propylene and at least one other gas, such as olefin, and/or a carrier gas, such as hydrogen or nitrogen. In the embodiment of the invention gas-phase polymerization is carried out in the mode of condensation.

In a variant of the embodiment of the invention, the contact occurs at a flow catalytic composition in a polymerization reactor and the introduction of the olefin in a polymerization reactor. In the embodiment of the invention the process includes providing contact of the olefin with socialization. Acetalization is miscible with the composition of pronatalistic (forces) before the introduction of the composition of pronatalistic in a polymerization reactor. In another embodiment, the invention socialization add in a polymerization reactor, regardless of the composition of pronatalistic. Independent introduction of socializaton in a polymerization reactor can occur simultaneously or essentially simultaneously with the filing of the composition of pronatalistic.

In the embodiment of the invention, the process includes mixing or otherwise combining the M-EED with the composition of pronatalistic. M-EED can be connected complex relationships with socialization and/or mixed with the composition of pronatalistic (formecu) before making contact between the catalyst composition and propylene. In another embodiment of the invention M-EED (or its individual components) can be entered independently in the polymerization reactor.

In the embodiment of the invention, the polymerization process includes maintaining the molar ratio of hydrogen to propylene ("H₂/S₃") is less than 0,30 (i.e. to 0.30:1) or less of 0.20 or less of 0.18 or less of 0.16 or less of 0.08 in the first reactor. Although high flow index is aspreva can be achieved by using high concentrations of hydrogen, it was found that based polymers of propylene obtained when a molar ratio of H₂/C₃more 0,30 accelerate unwanted reaction of the hydrogenation of propylene in the presence of oxidized carbon steel reactor and reduce the catalytic activity. On the other hand, the formed polymer based on propylene obtained by the method according to the present invention, does not have excessive amounts of catalyst residues, as the molar ratio of H₂/C₃is less than 0.3.

Furthermore, the low molar ratio of H₂/C₃while this value is less than 0,30, improves the performance of the catalyst. Increasing the value of molar ratio of H₂/C₃more hydrogen displaces large amounts of propylene. The substitution of hydrogen propylene reduces the amount of propylene, available for reaction with the catalyst composition. Thus, a large molar ratio of H₂/C₃indicates that polymerization fewer propylene. Less propylene, available for the reaction proceeds in a smaller amount of the resulting polymer is an indication of a decrease in catalyst activity and productivity of the catalyst.

On the contrary, the present catalyst composition provides the image is of a polymer based on propylene with a high melt flow index at low molar ratio of H ₂/C₃namely a molar ratio of H₂/C₃less than 0.3. Thus, the improved response of the hydrogen present composition of the catalyst improves the catalytic activity and improves performance.

In the embodiment of the present invention, the polymerization process includes maintaining the partial pressure of hydrogen below about 80 psi or below approximately 71 psi or below about 63 psi.

In the embodiment of the invention the process includes self-limiting polymerization process, when the temperature in the reactor is greater than about 100°C.

In the embodiment of the invention the process includes the formation of a polymer based on propylene in a single polymerization reactor.

The inventors have unexpectedly found that the presence of a mixed external electron donor provides a catalytic composition, which is self-limiting and produces a polymer based on propylene with high rigidity and high melt flow index in a single polymerization reactor under standard conditions of polymerization. Not wishing to be bound by any particular theory, the inventors believe that ALA improves process flexibility in a polymerization reactor is by preventing acceleration of the reaction, listomania polymer and/or agglomeration of the polymer caused by the action of excessive heat. Provision of SCA1 and SCA2 contributes to the development of high rigidity (i.e. T_MFmore than 170°C)/high fluidity of the melt (i.e. more than 50 or 60, or 70, or 100 g/10 min) polymer based on propylene using standard levels of hydrogen content.

In particular, this process mainly provides education-based polymer of propylene with high rigidity and high fluidity of the melt without light cracking the traditional method to increase MFR beyond the limitations of the use of hydrogen upon receipt of the polymer reactor type based on propylene with high rigidity, as discussed above. The term "light cracking" (or "cracking"), used herein, refers to thermal and/or chemical destruction of the polymer on the polymer chain segments of shorter length. Light cracking usually includes the transfer of the polymer (such as polypropylene) in the molten state in the presence of an initiator of free radicals (such as peroxide) with degradation of polypropylene shorter polypropylene chain segments. Light cracking is postreactor operation. It is clear that this method of obtaining the propylene impact copolymer is vnutrimatern the manner of polymerization. Thus, the present method of obtaining a propylene impact copolymer does not include a light cracking.

Light cracking has many side effects such as the formation of decomposition products (which often cause odor and incompatibility issues with food products), additional costs and the lowering of the rigidity of the polymer. Light cracking increases the fluidity of the melt, but reduces the mass-average molecular weight of the polymer. Light cracking alter the physical and chemical structure of the original polymer. For example, graciously polypropylene homopolymer will show a decline in physical and/or mechanical properties (i.e. to give a lower modulus of elasticity tensile, lower modulus of elasticity in bending) compared to nakikiramay propylene homopolymers with the same MFR value.

In the embodiment of the invention the method according to the present invention provides education Nekrestyanov polymer based on propylene. The polymer, which is "nakikiramay"are not subjected to the operation of a light cracking. In other words, nakikiramay polymer is not thermally and/or chemically destructionism polymer. Nakikiramay the polymer does not show reduction of physical and/or mechanical properties associated with the molecular weight is Oh (such as the modulus of elasticity in bending and/or strength properties), what is typical for recerving polymer with the same amount of MFR. In addition, nakikiramay polymer not exposed to the decomposition products (which often cause odor and incompatibility issues with food).

In the embodiment of the invention the method includes the formation of a polymer based on propylene with one or more of the following properties: (i) secretarially a propylene homopolymer; (ii) MFR greater than 50 g/10 min or greater than 60 g/10 min, or greater than 70 g/10 min, or greater than 100 g/10 min; (iii) soluble in xylene substances less than 4 wt.% or less than 3 wt.%, or from about 0.1 wt.% to less than 2.0 wt.%; (iv) T_MFmore about 165°C. or more and 170°C, (v) the content of ALA, at least from about 5 mln to approximately 150 mln, (vi) content postreactor oligomer ("oligomers" are₁₂-C₂₁connection) less than 3000 mln or less than 2500 mln, or from about 500 mln to approximately 3000 mlnc; and/or (vii) contents postreactor oligomer of about 10% or about 20%, or approximately 40% less than the corresponding content of the oligomer polymer based on propylene formed by the catalytic composition, which contains a composition that increases the rigidity of the SCA (and ALA) under the same conditions of polymerization. The term "content postreactor oligomer"used herein means the content of the oligomer formed from a polymer based on propylene immediately after exiting a polymerization reactor. In other words, "content postreactor oligomer" is the content of the oligomer to any operation paleolibertarians washing, operation of heating and/or cleanup operations.

In the embodiment of the invention nakikiramay polymer based on polypropylene is a propylene homopolymer. In another embodiment of the invention the polymer based on propylene has a low toxicity or no toxicity, low content of decomposition products or their absence and low smell or no smell.

In the embodiment of the invention, the active polymer based on propylene can be obtained, as disclosed in pending simultaneous consideration of the application (law docket No. 68316), filed February 21, 2009, the entire contents of which put into this document by reference.

The method according to the present invention includes the introduction of active polymer based on propylene in the second polymerization reactor. In the embodiment of the invention the first polymerization reactor and the second polymerization reactor work placentas is positive, resulting stream coming from the first polymerization reactor, download the second polymerization reactor and add one or more additional (or different) olefinic monomer in the second polymerization reactor to continue the polymerization process. In another embodiment of the invention each of the first polymerization reactor and the second polymerization reactor is a gas phase polymerization reactor.

The method includes providing contact active polymer based on propylene of at least one olefin in the second polymerization reactor under the conditions of polymerization and the formation of a propylene impact copolymer having a melt flow index more than about 60 g/10 min, measured according to ASTM D1238-01. At least one olefin comprises olefin different from propylene.

In the embodiment of the invention the method includes obtaining active polymer based on propylene with a value of more than 160 MFR g/10 min and obtaining a propylene impact copolymer with a MFR value more than about 85 g/10 min In another embodiment of the invention the method includes obtaining active polymer based on polypropylene with a MFR value is greater than 200 g/10 min and obtaining propylene darepro the aqueous copolymer with an MFR value more than about 100 g /10 min In another embodiment of the invention the method includes obtaining active polymer based on polypropylene with a MFR value more than about 300 g/10 min and obtaining a propylene impact copolymer with a MFR value more than about 150 g/10 minutes

Propylene impact copolymer is a heterophase copolymer. As used herein, "heterophase copolymer" is a multiphase polymer having a continuous polymer phase (also called phase matrix and the dispersed polymer phase (also called the elastomeric phase or rubber phase or rubber), dispergirovannoyj within a continuous polymer phase. The polymer based on propylene obtained in the first reactor is a continuous phase. Olefin is polymerized in the presence of a polymer based on propylene in the second reactor and forms a dispersed phase. Heterophase copolymer can contain more than two polymer phases.

The olefin introduced into the second reactor may be propylene, ethylene,_4-20α-olefin such as 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 1-hepten, 1-octene, 1-mission 1-dodecene and the like) or any combination thereof. In the embodiment of the invention propylene and ethylene in contact with the active polymer based on propylene in the second reactor with the formation of propylene case the face-to-face copolymer with a copolymer of propylene/ethylene as the dispersed phase.

In a variant of the invention, the propylene impact copolymer has a value of F_Cfrom about 5 wt.% to about 50 wt.% or from about 10 wt.% to about 40 wt.%, or from about 20 wt.% to about 30 wt.%. As used herein, "percentage of copolymer ("F_C"represents the mass percentage of the dispersed phase present in the heterophase copolymer. The value of F_Cbased on the total weight of the propylene impact copolymer.

Propylene impact copolymer may have an Ec value from about 20 wt.% to about 90 wt.% or from about 30 wt.% to about 80 wt.%, or from about 40 wt.% to about 60 wt.%. As used herein, "ethylene content" ("Ec") represents the mass percentage of the ethylene contained in the dispersed phase propylene impact copolymer. The Ec based on the total weight of the dispersed (or rubber) phase.

In one of the embodiments of the invention, the polymerization process includes maintaining the molar ratio of hydrogen to propylene ("H₂/S₃") less than 0.3 in the first polymerization reactor and/or the second polymerization reactor. It was found that based polymers of propylene obtained is passed at a molar ratio of N ₂/S₃more than 0,3 contain excessive amounts of residual catalyst, such as titanium or chlorine. The resulting polymer based on propylene, obtained according to the present method, devoid of excess residue of the catalyst, as the molar ratio of N₂/S₃is less than 0.3.

In another embodiment of the invention, the method includes maintaining the molar ratio of N₂/S₃less than 0.10 or less of 0.08 or less than 0.04, or less than 0.03 in the second polymerization reactor. Applicants unexpectedly found that maintaining a molar ratio of N₂/S₃less than 0.3 (and/or the molar ratio of N₂/S₃less than 0.1 in the second reactor) reduces the hydrogen consumption and improves the catalytic activity, since the presence of smaller amounts of hydrogen reduces the partial pressure of propylene and/or another olefin.

Not limited to any particular theory, the inventors believe that the composition of the catalyst according to the present method contributes to low levels of volatile components in the formed high impact propylene copolymer. In one of the embodiments of the invention the method includes the formation of a propylene impact copolymer having a content of volatile components is less than about 65 μg/g As is used in this document "volatile components" are carbon-containing substances that are released from the polymer in the form of a vapor at room temperature or slightly elevated temperatures. The content of volatile substances is less than about 65 μg/g or less than about 60 μg/g, or less than about 50 μg/g, or from about 10 μg/g to less than about 65 μg/g volatile solids set according to the standard Volkswagen (VW) PV 3341.

Low amount of volatile substances contained in this high impact propylene copolymer, significantly reduces or eliminates the procedure of cleansing purge. Ordinary propylene impact copolymer usually requires purging with nitrogen and/or steam blowdown (for several days) to reduce the volatile content to acceptable levels - especially for applications requiring a low content of volatile compounds, such as use as a food container. Low content of volatile compounds in this high impact propylene copolymer reduces the time cleaning purge or even eliminates the purge procedure.

In one of the embodiments of the invention the method comprises a self-limiting reaction of polymerization when the temperature is above 100°C in the first poly is erization the reactor and/or the second polymerization reactor. Not wanting to connect to any specific theory, the inventors believe that ALA improves process flexibility polymerization reactor by preventing the reverse flow of the reaction, separation of the polymer and/or agglomeration of the polymer due to the excessive heat generated during polymerization in any of the reactors.

In one of the embodiments of the invention the method includes the introduction of the M-EED or one or more of its components in the second reactor. Thus, the first selective agent regulation (SCA1), a second selective agent regulation (SCA2) and/or the agent that limits activity (ALA), can be added to the second reactor separately or in combination.

The method can comprise two or more embodiments of the invention described in this document.

This description applies to the other way. In one of the embodiments the invention relates to a method of polymerization which comprises effecting contact in a polymerization reactor under the conditions of polymerization of at least one olefin with an active polymer based on propylene. Active polymer based on polypropylene has a melt flow index of less than 100 g/10 minutes

The method further includes the formation of a propylene impact copolymer having until the choke melt, at least 85 g/10 min, measured in accordance with ASTM D-1238-01 (230°C, the weight of 2.16 kg). In one of the embodiments of the invention the polymer based on propylene MFR has more than about 150 g/10 min, and the propylene impact copolymer has an MFR greater approximately 100 g/10 min In another embodiment, the invention is a polymer based on propylene MFR has more than about 200 g/10 min, and the propylene impact copolymer has an MFR greater about 150 g/10 minutes

In one of the embodiments of the invention, the polymerization occurs by polymerization in the gas phase. In other words, the contact between the active polymer based on propylene and olefin(s) occurs in the gas-phase polymerization reactor under the conditions of polymerization. The polymerization reactor can be a second polymerization reactor, as described above.

In one of the embodiments of the invention, the method includes maintaining the molar ratio of N₂/S₃less of 0.20 or less than 0.10, of 0.08 or less, or less than 0.04, or less than 0.03 during the formation of propylene impact copolymer.

In one of the embodiments of the invention the method includes the self-limiting polymerization catalyst composition, is introduced into the active polymer based on propylene, when the temperature in polymerizati nom the reactor in excess of about 100°C. The catalyst is maintained in the active polymer based on propylene, can be the catalyst composition described herein, including precatalysts, socialization and a mixed external electron donor (M-EED)comprising the first agent selective regulation (SCA1), a second selective agent regulation (SCA2) and the agent that limits activity (ALA).

In one of the embodiments of the invention the method comprises introducing into the reactor M-EED or one or more of its components. Thus, the first selective agent regulation (SCA1), a second selective agent regulation (SCA2) and/or the agent that limits activity (ALA), can be introduced into the polymerization reactor separately or in any combination.

In one of the embodiments of the invention, the active polymer based on propylene in contact with propylene and ethylene. The method includes the formation of a propylene impact copolymer with a value of Fc from about 5 wt.% to about 50 wt.% and with the value of E_Cfrom about 20 wt.% to about 90 wt.%.

In one of the embodiments of the invention the method comprises mixing in the melt nucleating agent with a high impact propylene copolymer and formation containing a nucleating agent for the crystallization of propylene shock the selected copolymer. As used herein, "mixing in the melt is a process in which the polymer is softened and/or melted and mixed with one or more other compounds. Non-limiting volume of claims examples of the mixing of the melt include extrusion, the mixture melts (periodic or continuous), the reaction mixture from the melt and/or compounding.

The nucleating crystallization reduces the size of the crystallites, thus improving the transparency and purity of the products obtained from the propylene impact copolymer. Not wishing to be bound to any specific theory, the inventors believe that the crystallization nucleating centers provide for a more orderly and rapid crystallization of polyolefins during cooling. During the process of crystallization of the polymer crystals are arranged in two large CNT superstructure, called spherulites. Spherulites are more uniform and smaller in size than the crystals obtained in the absence of a crystallization nucleating agent.

Can be used without limitation various well-known in the art, the nucleating crystallization. Non-limiting volume of claims examples of suitable nucleating crystallization include benzoate intothree is, adipat aluminum; aluminum p-tert-butylbenzoate; derivatives arbitrates, such as 1,3,2,4-dibenzylideneacetone, 1,3,2,4-bis(p-methylbenzylidene)sorbitol, 1,3,2,4-bis(p-ethylaniline)sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene, 1,3-O-2,4-bis(3,4-dimethylbenzylidene)sorbitol (available from Milliken Chemical, Spartanburg, SC under the trade name Millad® 3988), 1,3-O-2,4-bis(p-methylbenzylidene)sorbitol (also available from Milliken Chemical under brand name Millad® 3940); bis(4-tert-butylphenyl)phosphate; bis(4-tert-were)phosphate sodium bis(4,6-di-tert-butylphenyl)phosphate, sodium 2,2'-methylene-bis(4,6-di-tert-butylphenyl)sodium phosphate (NA-11); 2,2'-ethylidene-bis(4,6-di-tert-butylphenyl)phosphate sodium; talc; calcium carbonate, and any combination of the aforementioned compounds.

In one of the embodiments of the invention the method includes the formation of a propylene impact copolymer having a content of volatile substances less than about 65 μg/g volatile solids is less than about 65 μg/g or less than about 60 μg/g, or less than 50 μg/g, or from about 10 μg/g to less than about 65 μg/g

The method can comprise two or more embodiments described herein.

The present description refers to the impact resistant polypropylene copolymer. Propylene impact resistant FOSS is emer includes a polymer based on propylene (phase matrix) and a copolymer of propylene/ethylene (dispersed phase), dispersed in it. The polymer based on propylene MFR has more than about 100 g/10 min Propylene impact copolymer has a melt flow index more than about 60 g/10 min, the value of Fc from about 5 wt.% to about 50 wt.%, the Ec value from about 20 wt.% to about 90 wt.%.

In one of the embodiments of the invention the polymer based on propylene MFR has more approximately 160 g/10 min, and the propylene impact copolymer has an MFR greater about 85 g/10 min In another embodiment, the invention is a polymer based on propylene MFR has more than about 200 g/10 min, and the propylene impact copolymer has an MFR greater approximately 100 g/10 minutes In one of the embodiments of the invention the polymer based on propylene MFR has more than about 300 g/10 min, and the propylene impact copolymer has an MFR greater about 150 g/10 minutes In another the embodiment of the invention the polymer based on propylene is polypropylene homopolymer.

In one of the embodiments of the invention the polymer based on propylene has one or more of the following properties: soluble in xylene substances less than 4 wt.% or less than 2 wt.%, and T_MFmore about 170°C.

In one embodiment, implementation of the program of the invention the polymer component is a propylene impact copolymer is not kreiranim. In other words, the propylene impact copolymer is nakikiramay, a polymer based on propylene is nakikiramay, and a copolymer of propylene/ethylene is nakikiramay.

In one variant of the invention, the propylene impact copolymer has a content of volatile substances is less than 65 μg/g or less than about 60 μg/g, or less than about 50 μg/g, or from about 10 μg/g to less than about 65 μg/g (VW PV3341).

In one variant of the invention, the propylene impact copolymer has a content of ALA at least 5 mln, or at least 10 mln, or at least 20 mln, or at least 30 mln, or from about 5 mln to approximately 150 mlnc

In one variant of the invention, the propylene impact copolymer is a containing a nucleating agent for the crystallization of the propylene impact copolymer.

Propylene impact copolymers of the present invention can be used in various applications, such as interior trim of the car where you want low volatile compounds, and can be used in various fields for the manufacture of articles intended for contact with food products, such as slid the key and containers. In addition, many conventional molded products, such as toys, buckets, pallets and products General purpose, can be realized the advantages of the material based on high impact propylene copolymer of the present invention with a high melt flow index, impact resistance and/or low content of volatile compounds. Propylene impact copolymer according to the invention can also be used to produce fibers for carpets, upholstery and diapers.

Propylene impact copolymer may comprise two or more embodiments of the invention disclosed in this document.

Definition

All references to the Periodic table of the elements herein shall refer to the Periodic table of the elements, published and copyrighted CRC Press, Inc., 2003. In addition, any references to the group or groups will be treated to a group or groups as reflected in this Periodic table of the elements using the IUPAC system for digital designation of groups. If not stated otherwise, are not expressed explicitly in the context of, or received in this area, all parts and percentages are calculated by weight. For the purposes of patent practices of the United States of America the contents of any patent, patent applications and publications cited therein, are ssy is coy in its entirety (or the equivalent of its American version is introduced by reference), especially with regard to the substance of the synthesis methods, definitions (to the extent not inconsistent with any of the definitions presented in this document) and universal knowledge in this field.

The term "comprising" and its derivatives are not intended to exclude the presence of any additional component, step or operation, regardless of whether she disclosed herein or not. To avoid any doubt, all of the compositions claimed herein through the use of the term "comprising"may include any additional additive, auxiliary substance or compound, polymer or otherwise, unless otherwise noted. In contrast, the term "consisting essentially of" excludes from the scope of the claims of any successful reference to any other component, step or operation, excluding those that are not important for flexibility. The term "consisting of" excludes any component, phase or operation not specifically defined or listed. The term "or", unless otherwise specified, refers to these elements individually or in any combination.

Any digital interval specified herein includes all values from the lowest value to the highest value with increments of one unit provided that there is a section who s in, at least 2 units between any lower value and higher value. As an example, if you specify that the component quantity or amount of a composition or physical properties, such as, for example, the quantity of the component in the mixture, the softening temperature, the melt index, etc. is a value between 1 and 100, it is assumed that all individual values, such as 1, 2, 3, etc. and all subranges such as from 1 to 20, from 55 to 70, from 197 to 100 and so on, are clearly listed in the application. For values that are less than one, a single unit if necessary, is considered to 0.0001 to 0.001, 0.01 or 0.1. These are just examples of what was implied, and all possible combinations of digital values between the lowest value and the highest of these values should be regarded as clearly specified in the application. In other words, any digital interval, cited herein, includes any value or subrange within the specified interval. Digital intervals specified, as discussed in this document, for standard melt index, melt flow index and other properties.

The term "mixture" or "polymer blend", as used herein, refers to a mixture of two or more polymers. This mixture may or may not be compatible (without FA the new division at the molecular level). This mixture may or may not be divided into phases. This mixture may contain or may not contain one or more configurations of domains, as determined by electron microscopy, scattering, scattering of x-rays and other methods known in this field.

The term "composition", as used herein, includes a mixture of materials, which includes the song, and also the reaction products and decomposition products formed from the materials of the composition.

The term "polymer" refers to a macromolecular compound obtained by polymerization of monomers of the same or of different types. "Polymer" includes homopolymers, copolymers, triple polymers, interpolymer, etc. the Term "interpolymer" refers to a polymer obtained by polymerization of at least two types of monomers or copolymers. It includes, but is not limited to, copolymers (which usually refers to polymers derived from two different types of monomers or comonomers), triple polymers (which usually refers to polymers derived from three different types of monomers or comonomers), terpolymer (which usually refers to polymers derived from four different types of monomers or comonomers), etc.

The term "interpolymer", as used herein, refers to polim the frames, obtained by polymerization of at least two monomers of different types. Thus, the General term interpolymer includes copolymers, commonly used to refer to polymers derived from two different monomers, and polymers derived from more than two monomers of different types.

The term "polymer-based olefin" refers to a polymer containing in polymerized form the main mass percentage of the olefin, for example ethylene or propylene, based on the total weight of the polymer. Non-limiting creatures of the invention, examples of polymers based on olefins include polymers based on ethylene-based polymers of propylene.

The term "polymer based on ethylene", as used herein, refers to a polymer that includes a primary mass percentage of polymerized monomer ethylene (based on the total weight of polymerized monomers), and optionally may include at least one polymerized comonomer.

The term "interpolymer ethylene/α-olefin"as used herein refers to interpolymer, which includes a primary mass percent polymerized ethylene monomer (based on the total amount of polymerized monomers) and at least one polymerized α-olefin.

The term "polymer based on polypropylene" as used in the present invention, refers to a polymer that includes a primary mass percent polymerized propylene monomer (based on the total amount of polymerized monomers), and optionally may include at least one polymerized comonomer.

The term "alkyl", as used herein, refers to a branched or unbranched, saturated or unsaturated acyclic hydrocarbon radical. Non-limiting volume of claims examples of suitable alilovic radicals include, for example, methyl, ethyl, n-propyl, isopropyl, 2-propenyl (or allyl), vinyl, n-butyl, tert-butyl, isobutyl or 2-methylpropyl), etc. alkili have from 1 to 20 carbon atoms.

The term "substituted alkyl"used herein refers to alkyl, just described above, in which one or more hydrogen atoms associated with carbon atom of the alkyl is replaced by another group such as halogen atom, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, heteroseksualci, substituted heteroseksualci, halogen, halogenated, hydroxy, amino, phosphino, alkoxy, amino, thio, nitro, and combinations thereof. Suitable substituted alkali include, for example, benzyl, trifluoromethyl, etc.

The term "aryl"used herein refers to aromatic Deputy, who may represent a single aromatic ring or multiple aromatic rings, are condensed with each other, connected by covalent bonds or connected to a common group such as a methylene or ethylene group. The aromatic ring(s) may include phenyl, naphthyl, anthracene and biphenyl, among others. Arily have from 1 to 20 carbon atoms.

Test methods

The modulus of elasticity in bending are determined according to standard ASTM D790-00 Method 1, using a sample for testing according to ASTM D 638 type 1 at a speed of 1.3 mm/min

Impact strength Izod measured according to ASTM D256.

The melt flow index (MFR) measured according to the method of testing according to ASTM D 1238-01 at 230°C, with a weight of 2.16 kg of the polymer based on propylene.

Soluble in xylene substances (XS) is measured by the following method: 0.4 g of polymer was dissolved in 20 ml of xylene under stirring at 130°C for 30 minutes. Then the solution is cooled to 25°C and after 30 minutes the fraction of nerastvorimogo polymer is filtered off. The obtained filtrate is analyzed by the method of flow injection polymer using column Viscotek ViscoGEL H-100-3078 with mobile phase THF, flowing with a speed of 1.0 ml/min Column is connected with the detector matrix with double frequency conversion Viscotek Model 302 with the detector light scattering, viscometer and a Refractometer operating at 45°C. the Calibration of p is ibrow support using polystyrene standards Viscotek PolyCAL™.

The final melting temperature T_MFis the temperature necessary for melting the preferred crystal in the sample, and is considered a measure of isotacticity and characterization of crystallinity of the polymer. The test is carried out using a differential scanning calorimeter (TA Q100. The sample is heated from 0°C to 240°C at 80°C min, cooled at the same speed to 0°C, then re-heated at the same rate up to 150°C, maintain at 150°C for 5 minutes and heated from 150°C to 180°C at the rate of 1.25°C/min, T_MFdetermined by the last cycle by calculating the beginning of the baseline at the end of the heating-up curve.

Test method

(1) Calibrate the instrument on India high purity as standard.

(2) Pull the head/camera device with nitrogen at a constant speed of 50 ml/min

(3) Preparation of sample:

Pressed 1.5 g of powdered sample on the press 30-G302H-18-CX, Wabash Compression Molder (30 tons): (a) heat the mixture at 230°C for 2 minutes in the mold; (b) pressing the sample at the same temperature under a pressure of 20 tons for 1 minute; (C) cooling the sample to 45°F and hold for 2 minutes under a pressure of 20 tons; (d) cut the plate into 4 pieces approximately the same size, connect them together and repeat stage (a)(C)to homogenize the sample.

(4) Take a portion of the sample (site is preferably between 5 and 8 mg) and close it in standard aluminum cell for the sample. Put a closed cell containing the sample, the sample head/cell device and put an empty closed cell on the side of the reference standards. If you use the automatic sampler, weigh several different test specimens from the sample and install the machine on the sequence of operations.

(5) Dimension:

(i) data Storage: off

(ii) a Rapid linear increase with speed 80,00°C/min to 240,00°C

(iii) Isothermal mode for min 1,00

(iv) Rapid change at 80°C/min to 0.00°C

(v) Isothermal mode for min 1,00

(vi) Rapid change with speed 80,00°C/min to 150.00°C

(vii) Isothermal mode for 5,00 min

(viii) data Storage: the inclusion of

(ix) a Rapid change with the speed of 1.25°C/min to 180,00°C

(x) the end of the measurements

(6) Payment: T_MFdetermined by the intersection point of two lines. One line is carried out from the baseline to the high temperature. Another line passes through the point of curvature closer to the end of the curve from high temperatures.

The content of volatile compounds measured by method static analysis of free space, described in the book "Pyrolysis and GC in Polymer Analysis", published S.A. Leibman and E.J. Levy, Marcel Dekker Inc., 1985. Method of gas chromatography/gas chromatography of free space (GC-HS) is widely used in the camping in the automotive industry. Volkswagen AG has developed a standard that is generally accepted and used in the plastics industry. Known as the "Standard VW PV 3341" (or "PV3341") PV 3341 is a test in which a sample weight of 2 grams is placed in free space capsules, condition for 5 hours at 120°C and then injected into the gas chromatograph. Quantification is performed using the method of external standard, based on the change of the acetone peak area of the standards.

Further examples will be provided on the merits of the present invention, which are merely examples and do not limit the invention.

Examples

(1) Precatalysts

SHAC 320 is composed of pronatalistic Ziegler-Natta consisting of titanium, magnesium and the internal electron donor of diisobutylphthalate obtained according to example 1 in U.S. patent No. 6825146, the entire contents of which are introduced in this document by reference.

Precatalysts FV is the composition of pronatalistic Ziegler-Natta consisting of titanium, magnesium and the internal electron donor is simple 1,3-diapir, as described in European patent application No. 728769. FV precatalysts obtained as described below.

When the ambient temperature combined 350 g mixed alcoholate of the halide of magnesium/titanium, 72 g of 9,9-bis(methoxymethyl)-N-fluorene 5.6 l 5050 mixture (about./about.) chloride titanium(IV) and chlorobenzene. The mixture was shaken at a temperature of 105-115°C for 60 min, allowed to settle and filtered at 100°C. the Solid was dissolved in 2.8 l of chlorobenzene at 85°C, allowed to settle and filtered at 85°C. the Solid was twice dissolved in 5.6 l of fresh 50/50 mixture of titanium chloride(IV) and chlorobenzene at 105-115°C for 30 min, allowed to settle and filtered at 100°C. After cooling, the solids washed twice with 5.2 liters of hexane at 50-60°C With subsequent final rinse 5.6 l 2-methylbutane at ambient temperature. The solids were combined with 1.19 kg of mineral oil, and the resulting suspension was subjected to vacuum treatment to remove residual volatiles.

(2) the External electron donors

Samples a-E included a mixed external electron donor (M-EED) with components M-EED, selected from among the following:

DCPDMS: dicyclopentadienyliron (SCA)

IPM: isopropylmyristate (ALA)

PTES: n-propyltriethoxysilane (SCA2)

TEOS: tetraethoxysilane (SCA2)

Sample F includes an external electron donor components, selected from among the following:

DCPDMS: dicyclopentadienyliron (SCA)

IPM: isopropylmyristate (ALA)

Samples G and H was the usual high-impact copolymers. Sample H was obtained with the composition of the catalyst, which included dicyclopentadienyliron as external to the ora of electrons. Samples G and H are given as comparative, and they are not variants of implementation of the present invention.

(3) Polymerization

Obtaining samples A-F and sample H was carried out in the gas phase using linked fluidized bed reactor as described in U.S. patent No. 4882380, the full content of which is introduced in the present document by reference. The polymerization conditions were those shown below in table 2.

Sample G was the usual high-impact copolymer obtained by the method Spheripol known multi-stage process using a polymerization reactor in the liquid phase in the first stage, followed by one or two additional reactors of the polymerization in the gas phase to obtain the rubber phase. The final product is the reactor type (i.e., not kreiranim).

At the last stage of receipt of samples A-F each of the samples were unloaded in a container and processed (or disabled) moist nitrogen at 22°C using approximately 3 kg of water per 1000 kg of resin for 3 hours.

After removing the resin sample N from the reactor it was disabled by blowing within 1-3 hours of moist nitrogen at 22°C using 1 kg of water at 1000 kg of polymer.

Samples A-F and H were mixed with the additives listed in table 4, using dvuhserijnyj extruders with vzaimozachety the m After mixing these samples were not subjected to any purging.

Samples A-F have a lower content of volatile substances than comparative sample H, despite the fact that each of samples A-F has a higher MFR than the sample N.

Sample F shows that when using other catalysts (FV catalyst) in combination with IPM and DCPDMS can be achieved the same result, namely obtaining a high impact propylene polymer with a high melt flow index and a low content of volatile substances. In addition, when using IPM in combination with DCPDMS (and possibly with other silanes), fewer DCPDMS, providing further cost reduction, as DCPDMS is more expensive.

Each of samples a and b has the same or essentially the same properties of impact resistance and stiffness as sample G (using essentially the same or similar additives). Surprisingly and unexpectedly, that the real propylene impact copolymer obtained in the gas phase, is superior in the content of volatile substances. In particular, each of the samples a and b has a lower content of volatile substances than the sample G.

In particular, it is understood that the present the invention is not limited herein variant implementation of the invention and the illustrations, but include modified forms of those embodiments of the invention, including embodiments of the invention and combinations of elements of different embodiments of the invention, as follows from the essence of the following claims.

1. The method of polymerization, including
the implementation of contact of propylene and optionally at least one other olefin with a composition of the catalyst in the first polymerization reactor under the conditions of polymerization in the gas phase, where the catalyst composition includes precatalysts, socialization and a mixed external electron donor (M-EED)comprising the first agent selective regulation (SCA1), a second selective agent regulation (SCA2) and the agent that limits activity (ALA);
education in the first polymerization reactor active polymer based on propylene having a melt flow index more than about 100 g/10 min, measured according to ASTM D1238-01 (230°C, 2,16 kg);
the implementation of contact of the active polymer based on propylene of at least one olefin in the second polymerization reactor under the conditions of polymerization, and
obtaining a propylene impact copolymer having a melt flow index more than about 60 g/10 minutes

2. The method according to claim 1, including maintaining the mod is popular ratio of N ₂/S₃less than 0.3 in one or both reactors.

3. The method according to claim 1, including maintaining the molar ratio of N₂/S₃less than 0.1 in the second polymerization reactor.

4. The method according to claim 1, comprising the introduction into the second reactor component selected from the group consisting of a mixed external electron donor (M-EED), the first selective agent regulation (SCA1), the second agent selective regulation (SCA2), agent, restricting activity (ALA) and their combinations.

5. The method according to claim 1, comprising effecting contact of the active polymer based on propylene to propylene and ethylene and obtaining the propylene impact copolymer having a value of Fc from about 5 wt.% to about 50 wt.% and the Ec value from about 20 wt.% to about 90 wt.%.

6. The method according to claim 1, comprising obtaining a propylene impact copolymer having a content of volatile compounds, less than about 65 μg/g, measured according to the standard VW PV3341.

7. The method according to claim 1, including the restraint of polymerization composition of the catalyst, when the temperature exceeds 100°C., in a reactor selected from the group consisting of the first polymerization reactor, the second polymerization reactor, and combinations thereof.

8. The method of polymerization, including
implementation is ontact in a polymerization reactor under the conditions of polymerization, at least one olefin with an active polymer based on propylene having a melt flow index more than about 100 g/10 min, measured according to ASTM D1238-01 (230°C, 2,16 kg), where the active polymer based on propylene includes a catalyst composition comprising precatalysts, socialization and a mixed external electron donor (M-EED)comprising the first agent selective regulation (SCA1), a second selective agent regulation (SCA2) and the agent that limits activity (ALA), obtaining a propylene impact copolymer having a melt flow index more about 85 g/10 minutes

9. The method according to claim 8, in which the active polymer based on propylene includes self-limiting composition of the catalyst, where the method includes the restraint of polymerization when the temperature in the polymerization reactor is greater than about 100°C.

10. Propylene impact copolymer obtained by the method according to claim 1, comprising a polymer based on propylene having a melt flow index (MFR) greater than about 100 g/10 min, measured according to ASTM D-1238-01 (230°C, 2,16 kg), a copolymer of propylene/ethylene, dispersed in a polymer based on propylene; and propylene impact copolymer has a melt flow index more than about 60 g/10 min, the proportion of the copolymer (Fc) from about 5 wt.% to about 50 wt.% and the ethylene content (Ec) from about 20 wt.% to about 90 wt.%.