Catalyst composition with mixed selectivity control agent and polymerisation method using said composition

FIELD: chemistry.

SUBSTANCE: invention relates to Ziegler-Natta catalysts. Described is a catalyst composition containing: Ziegler-Natta procatalyst composition containing titanium, magnesium and an internal electron donor, containing at least two oxygen-containing functional groups, the oxygen-containing functional groups being separated by at least one saturated C₂-C₁₀ hydrocarbon chain which can optionally contain a heteroatom; organoaluminium compounds as a cocatalyst; and a mixed external electron donor (M-EED) comprising an activity limiting agent (ALA), a first selectivity control agent (SCA1) containing an alkoxysilane, a second selectivity control agent (SCA2) selected from a group consisting of an alkoxysilane, a diether, and a dialkoxybenzene, wherein the molar ratio SCA1:SCA2 ranges from 0.1:1 to 1.0:1, the molar ratio of total-SCA to ALA is less than 1.0, and wherein the ALA is selected from a group consisting of an aromatic ester or a derivative thereof, an aliphatic ester or a derivative thereof, a diether, poly(alkylene glycol) of an ester and combinations thereof.

EFFECT: novel catalyst composition is described.

10 cl, 2 dwg, 8 tbl, 2 ex

The CLAIM TO PRIORITY

This bid is partially continuation application of international patent application no PCT/US2008/073882, filed August 21, 2008, which claims priority to provisional patent application U.S. No. 60/957888, filed August 24, 2007, the content of each application in their entirety by reference is incorporated herein.

PREREQUISITES

As the continuing growth of demand for more sophisticated polymers continues to grow and the need for the high rigid propylene polymers on the basis of the high fluidity of the melt. Known compositions of catalysts polymers with a mixture of agents that regulate the selectivity (ARS). Mixed ARS make it possible to obtain olefin polymers on the basis of that have the properties assigned to each APC. However, the use of the compositions of the catalysts with mixed ARS does not change vysokoekonomichny nature of the reaction of olefin polymerization. Excess heat generated during the polymerization, creates a significant risk facilities polymerization reactor in circulation. Excessive generation of heat and/or improper heat can interfere with the production and/or to stop the reactor.

Desirable would be the composition of the catalyst according to the teachings of the propylene polymers on the basis of, high rigidity/high fluidity of the melt, which reduces or eliminates the risk of breaking or reactor shutdown due to excessive heat.

SUMMARY of INVENTION

The present description discloses a catalyst composition and method of polymerization to obtain the polymer in propylene-based high speed melt flow and high rigidity. The composition of the catalyst is self-limiting and shows a strong response to hydrogen at getting under standard conditions of conducting polymerization of the propylene polymer basis, characterized by high fluidity of the melt/high rigidity.

The present description provides the composition of the catalyst. The catalyst composition includes a composition of pronatalistic, socialization and a mixed external electron donor (C-VDE). S-VDE enables the agent that limits activity (AOA), the first agent, governing the selectivity, (ARS), the second agent, governing the selectivity, (ARS). ARS and ARS are present in a molar ratio of 0.1 to 1.0:1.

In one embodiment, the AOA is chosen from aromatic ether complex or its derivative, aliphatic ether complex or its derivative, simple diapir, poly(alkylenglycol) of ester and combinations thereof.

In one embodiment, ARS choose from diethoxyethane, triethoxysilane, tetraethoxysilane, triethoxysilane, simple diapir, dialkoxybenzene, dimethoxysilane having two linear alkyl groups, dimethoxysilane having two alkeneamine group, and combinations thereof.

The present description of the invention offers a way. In one embodiment proposes a method of polymerization comprising the introduction of propylene and optionally at least one other olefin in contact with the catalyst composition in a polymerization reactor during polymerization. The catalyst composition includes precatalysts, socialization and VDE. The method further includes obtaining the propylene polymer basis, characterized by the rate of flow of the melt, is equal to at least 50 g/10 minutes

In one embodiment, the composition of the catalyst causes the restraint of the polymerization reaction.

The present description of the invention provides a composition. In one embodiment, features a propylene polymer basis, which includes at least 5 ppm of the agent, restricting activity. The propylene polymer of the base is characterized by the rate of flow of the melt, greater than about 50 g/10 min, as measured in accordance with to the a side with ASTM D 1238-01 at 230°C, of 2.16 kg

One advantage of the present description of the invention is to offer an improved catalyst composition.

One advantage of the present description of the invention is to propose an improved method of polymerization.

One advantage of the present description of the invention is to offer an improved propylene polymer basis.

One advantage of the present description of the invention consists in the proposal of composition of the catalyst, which leads to the production of the propylene polymer basis, characterized by high fluidity of the melt/high rigidity, while the composition of the catalyst causes the restraint of the polymerization reaction.

One advantage of the present description of the invention consists in the method of producing propylene polymer basis, characterized by high fluidity of the melt/high rigidity, with standard quantities of hydrogen without holding a light cracking.

One advantage of the present description of the invention consists in the proposal of the propylene polymer basis, characterized by high fluidity of the melt and having one or more of the following properties: high temperature end of melting, low levels of oligomers, low toxicity or her absence, the lower the level of content degradation products or their absence and/or mild odor or lack of it.

BRIEF DESCRIPTION of DRAWINGS

Figure 1 is a graph showing the temperature of the end of the melting and the rate of flow of melt to the propylene polymer basis.

Figure 2 is a graph showing the levels of oligomers and the rate of flow of melt to the propylene polymer basis.

DETAILED description of the INVENTION

In one embodiment, the proposed composition of the catalyst. The catalyst composition includes a composition of pronatalistic, socialization and a mixed external electron donor (C-VDE). S-VDE includes first agent, governing the selectivity (ARS), the second agent, governing the selectivity (ARS) and the agent that limits activity (AOA). S-VDE includes the molar ratio ARS:ARS in the range of from about 0.1:1 to approximately 1.0:1.

You must understand that WITH the rde may include three or more agents that regulate the selectivity, (ARS, ERS and the like) and/or two or more of the AOA.

The composition of proceduresfor the present catalyst composition may be a composition of pronatalistic Ziegler-Natta. In the present catalyst composition may be used any conventional precatalysts Ziegler-Natta. In one embodiment, the composition of pronatalistic Ziegler-Natta contains a compound of a transition metal is a and the compound of the metal is from group 2. The transition metal compound may be a solid complex produced from the compound of the transition metal, for example, hidrocarbonetos, hidrocarburos, halides of titanium, zirconium, chromium or vanadium or mixtures thereof.

The transition metal compound described by General formula TrX_xwhere Tr is a transition metal, X represents halogen or_1-10hydrocarbonbearing or hydrocarbonous group, and x represents the number of such groups X in the compound in combination with a compound of the metal is from group 2. Tr may be a metal from group 4, 5 or 6. In one embodiment, Tr represents a metal of group 4, such as titanium. X can be a chloride, bromide,_1-4the alkoxide or phenoxide or their mixture. In one embodiment, X is a chloride.

Non-limiting examples of suitable transition metal compounds that can be used to produce compositions of pronatalistic Ziegler-Natta represent TiCl₄, ZrCl₄, HfCl₄, TiBr₄, TiCl₃, Ti(OC₂H₅)₃Cl, Zr(OC₂H₅)₃Cl, Ti(OC₂H₅)₃Br, Ti(OC₃H₇)₂Cl₂, Ti(OC₆H₅)₂Cl₂, Zr(OC₂H₅)₂Cl₂and Ti(OC₂H₅)Cl₃. T is to be used and mixtures of such compounds of transition metals. A number of compounds of transition metals of any restrictions do not impose up until will be present, at least one compound of the transition metal. In one embodiment, the transition metal compound is a compound of titanium.

Non-limiting examples of suitable compounds of metals of group 2 include magnesium halides derived dialkoxybenzene, halides alkoxyamine, oxychloride magnesium derivative dialkylamino, magnesium oxide, magnesium hydroxide and carboxylates of magnesium. In one embodiment, the compound of the metal is from group 2 is a magnesium dichloride.

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

Non-limiting examples of suitable titanium compounds include titanium alkoxides, aryloxides titanium and/or titanium halides. Connection, use the iesa to obtain the composition of pronatalistic Ziegler-Natta, include one or more representatives from di(C_1-4)alkoxides of magnesium, dihalogenide magnesium, alkoxylated magnesium or mixtures thereof and one or more representatives from Tetra(C_1-4)alkoxides of titanium, tetrachloride titanium, (C_1-4)alkoxylation titanium or mixtures thereof.

To obtain the composition of pronatalistic Ziegler-Natta can be used in the composition of the precursor as it is commonly known at the present level of technology. The composition of the precursor can be obtained by chlorination of the above-mentioned mixed magnesium compounds, titanium compounds, or mixtures thereof and may include the use of one or more compounds called "clip agents, which facilitate receiving or solubilize specific compositions in the metathesis solid/solid. Non-limiting examples of suitable clip agents include trialkylborane, especially triethylborane, phenolic compounds, especially cresol, and silanes.

In one embodiment, the composition of the precursor is a mixed compound of magnesium/titanium, vpisivaushiesya formula Mg_dTi(OR_e)_fX_gwhere R_erepresents an aliphatic or aromatic hydrocarbon radical containing from 1 to 4 carbon atoms, or COR'where R' is an aliphatic or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms; each group OR_eis identical or different; X independently represents a chlorine, bromine or iodine; d is 0.5 to 56 or is 2-4; or 3; f is 2-116 or 5-15; and g is 0.5-116, or 1-3, or 2. The precursor can be obtained in the controlled deposition during the removal of alcohol from the reaction mixture, which is used when it is received. In one embodiment, the reaction medium comprises a mixture of aromatic liquids, in particular chlorinated aromatic compounds such as chlorobenzene, alkanols, in particular ethanol, and inorganic gloriouse agent. Suitable inorganic gloriouse agents include chlorinated derivatives of silicon, aluminum and titanium, such as titanium tetrachloride or trichloride titanium, in particular titanium tetrachloride. Gloriouse agents lead to incomplete chlorination, resulting in a precursor characterized by a relatively high content of alkoxy-component (components). Remove alkanol from the solution used in the chlorination, resulting in the precipitation of the solid precursor, characterized by desirable morphological the th and specific surface area. The precursor was separated from the reaction media. In addition, the resulting precursor is characterized by a particularly uniform particle size and resistance to staining particles and decomposition of the resulting pronatalistic. In one embodiment, the composition of the precursor represents the Mg₃Ti(OEt)₈Cl₂.

After the precursor is converted into solid precatalysts as a result of additional reactions (halogenation) with inorganic derivative halide, preferably a derivative of titanium halide, and the introduction of an internal electron donor. If it is not included in the predecessor in sufficient quantity, the internal electron donor may be added separately before, during or after halogenation. This technique can be repeated one or more times, optionally in the presence of additional additives or auxiliary substances, and the final solid product may be washed with an aliphatic solvent. Suitable for use in the present description of the invention is any method of obtaining, retrieving and storing of solid pronatalistic.

One suitable method of halogenation of the precursor is the reaction between the precursor when polysensitization and a halide of tetravalent titanium, optionally in the presence of hydrocarbon or galogenovodorodov diluent. The preferred halide of tetravalent titanium is a titanium tetrachloride. Optional hydrocarbon or halogenougljovodonika solvent used in obtaining 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 kalogeropoulou include methylene chloride, metropolit, chloroform, carbon tetrachloride, 1,2-dibromoethane, 1,1,2-trichloroethane, tricorcelexa, dichloromethan and tetrakhloretan. Examples of aromatic kalogeropoulou include chlorobenzene, Brabanthal, dichlorbenzene and chlorotoluene. Aliphatic halogenougljovodonika may be a compound having at least two chloride substituent, such as carbon tetrachloride or 1,1,2-trichloroethane. Aromatic halogenougljovodonika can be a chlorobenzene or o-chlorotoluene.

Halogenoalkane can be repeated one or more times, optionally with concomitant washing with an inert liquid, such as aliphatic or aromatic hydrocarbons is od or halogenougljovodonika, between galogenirovannami and after halogenation. In addition, to remove volatile substances, in particular TiCl₄not necessarily can be used one or more ekstragirovanie, including the introduction in contact with an inert liquid diluent, especially an aliphatic or aromatic hydrocarbon, in particular at elevated temperature greater than 100°C., or greater than 110°C.

In one embodiment, the composition of pronatalistic Ziegler-Natta includes a solid catalyst component obtained by (i) the suspension dialkoxybenzene in aromatic hydrocarbon or halogenougljovodonika, which are liquid at normal temperatures, (ii) the introduction of dialkoxybenzene in contact with the titanium halide and, in addition, (iii) introducing the resulting composition a second time in contact with the titanium halide and the introduction dialkoxybenzene in contact with complex fluids aromatic dicarboxylic acid at some point in time during the processing of the titanium halide in position (ii).

In one embodiment, the composition of pronatalistic Ziegler-Natta includes a solid catalyst component obtained by (i) the suspension of the material predecessor, opisyvayushchego formula Mg_dTi(OR_e)_fX_g, (described to enter is) in an aromatic hydrocarbon or halogenougljovodonika, which are liquid at normal temperatures, (ii) the introduction of the precursor into contact with a titanium halide and, in addition, (iii) introducing the resulting composition a second time in contact with the titanium halide and the introduction of the precursor into contact with complex fluids aromatic dicarboxylic acid at some point in time during the processing of the titanium halide in position (ii).

The composition of pronatalistic includes an internal electron donor. In accordance with the usage in this document "the internal electron donor is a compound added to or otherwise received during the receiving of the composition of pronatalistic, which gives (gives) a pair of electrons to one or more metals present in the resulting composition pronatalistic. It is believed, without binding itself to any specific theory, the internal electron donor contributes to the regulation of the formation of active sites, thereby, improve the stereoselectivity of the catalyst.

In one embodiment, the internal electron donor is a bidentate compound. "Bidentate compound in accordance with use herein is a compound having at least two oxygen-containing functional of the groups, when this oxygen-containing functional groups separated by at least one saturated With₂-C₁₀hydrocarbon chain, which optionally may contain heteroatom (heteroatoms). Bidentate compound may be a phthalate, simple fluids, succinate, phenylendiamin, maleinate, malonate, glutarate, dialkoxybenzene, bis(alkoxyphenyl), diology ester, complex keeeper, alkoxyalkyl ester, bis(alkoxyalkyl)fluoran and any combination thereof.

In one embodiment, the internal electron donor is a phthalate, including diisobutylphthalate and/or di-n-butylphthalate.

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

In one embodiment, the internal electron donor is phenylendiamin.

The composition of pronatalistic Ziegler-Natta may also include an inert carrier material. The carrier may be an inert solid substance that does not change adversely catalytic performance of the compound of the transition metal. Examples include metal oxides, such as alumina, and oxides of metalloids, such as silicon dioxide.

The present catalyst composition includes socialise the op. Acetalization designed for use in conjunction with the above composition pronatalistic Ziegler-Natta, can be an aluminium-containing composition. Non-limiting examples of suitable aluminium-containing compositions include alyuminiiorganicheskikh compounds such as derivatives trialkylamine, dialkylaminomethyl, alkylamineacetate, dialkylaminoalkyl, alkylhalogenide, dialkylaminoalkyl and alkylamidoamines containing 1-10, or 1-6 carbon atoms in each alkyl or alkoxide group. In one embodiment, socialization is a derivative of₁-₄trialkylamine, such as triethylamine (tea or TEAL). The molar ratio of aluminum and titanium is 10-200:1 or 35 to 50:1. In one embodiment, the molar ratio of aluminum and titanium is 45:1.

The present composition of the catalyst comprises a mixed external electron donor (C-VDE), which includes the first agent, governing the selectivity, (ARS), the second agent, governing the selectivity, (ARS) and the agent that limits activity (AAO). In accordance with the usage in this document "external electron donor" (or "RDE") is a compound that is added regardless of education pronatalistic,which has at least one functional group which is able to give a pair of electrons to the metal atom. It is believed, without binding itself to any particular theory, the presence of one or more external electron donor in the catalyst composition has an impact on the following properties of the resulting polymer: the level of tact (i.e., the level of content material, soluble in xylene), molecular weight (i.e., the fluidity of the melt), molecular mass distribution (MMD), melting point and/or the content of oligomers.

Non-limiting examples of suitable compounds in respect of ARS include silicon compounds such as alkoxysilane; ethers and polyethers, such as alkalemia, cycloalkyl, arrouye, mixed alkyl/akrilovye, mixed alkyl/cycloalkyl and mixed cycloalkyl/akrilovye ethers, and/or polyethers; esters and polyesters, in particular alkalemia, cycloalkyl and/or akrilovye esters of monocarboxylic or dicarboxylic acids, such as aromatic monocarboxylic or dicarboxylic acid; based on Akilova or cycloalkyl simple ether or simple tiefere derivatives of such esters or polyesters, such based Akilova simple broadcast PR is spodnie alilovic esters or complex diesters of aromatic monocarboxylic or dicarboxylic acids; and replaced by a heteroatom from group 15 or 16 all derivatives of the aforementioned compounds; and amine compounds such as cyclic, aliphatic or aromatic amines, more specifically, pyrrole and pyridine compounds; all of the above ARS contain from 2 to 60 carbon atoms in the aggregate and from 1 to 20 carbon atoms in any alkyl or alkilinity 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 one embodiment, ARC and/or ERS is a silane composition described General formula (I):

SiR_m(OR')_4-m(I)

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 group, and m is 0, 1 or 2. In one embodiment, R represents a C_6-12aryl, alkyl or Uralkaliy,_3-12cycloalkenyl,_3-12branched alkyl or C_3-12the cyclic amino group, R' represents a C_1-4alkyl, and m costal is no 1 or 2.

In one embodiment, AS is dimethoxysilane. Dimethoxysilane may include dimethoxysilane having at least one secondary alkyl and/or secondary amino group directly related to the silicon atom. Non-limiting examples of suitable dimethoxysilane include dicyclopentadienyliron, methylcyclohexylamine, diisobutyldimethoxysilane, isopropylidenedicyclohexanol, diisobutyldimethoxysilane, tert-utilizationfocused, cyclopentylpropionate, bis(pyrrolidino)dimethoxysilane, bis(perhydrosqualene)dimethoxysilane and any combination of the above-mentioned compounds.

In one embodiment, ART is a composition promoting rigidity. "Composition, promoting rigidity" in accordance with the use herein is a composition, which, when the operations of the respective process conditions of the present description of the invention, enhance or otherwise improve the rigidity of the polymer, resulting in the required conditions of the polymerization. Non-limiting examples of suitable promotion stiffness include any of the aforementioned dimethoxysilane.

In one embodiment, AS is dicyclo interdimensional.

In one embodiment, ART is a compound of silicon selected from diethoxyethane, triethoxysilane, tetraethoxysilane, triethoxysilane, dimethoxysilane having two linear alkyl groups, dimethoxysilane having two alkeneamine group, simple diapir, dialkoxybenzene and any combination thereof.

Non-limiting examples of suitable silicon compounds against ARS 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-methyldithiocarbamate)diphenylmethane, (3-glycidoxypropyl)metildigoxin, dodecyltriethoxysilane, dimethyldiethoxysilane, diethyldichlorosilane, 1,1-diethoxy-1-silacyclopentane-3-ene, chlorodimethylvinylsilane, bis(methyldeoxycytidine)amine, 3-AMI is propylmethyldimethoxysilane, (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, triethoxycaprylylsilane, (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-methylenedicyclohexyl, 3-methoxypropionitrile, methacryloxypropyltrimethoxysilane, methacryloxypropyl amoxicilan, methacryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane and O-(methacryloxyethyl)-N-(triethoxysilylpropyl)carbamate, tetramethoxysilane and/or tetraethoxysilane.

In one embodiment, AS can be methylcyclohexanecarboxylic, diisobutyldimethoxysilane, 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 one embodiment, ARS choose from dimethoxysilane having two linear alkyl groups, dimethoxysilane having two alkeneamine group or two hydrogen atoms, where one or more hydrogen atoms may be substituted with halogen, and any combination thereof.

In one embodiment, ARS can be simple fluids, dimer simple diapir, dialkoxybenzene, dimer of dialkoxybenzene, dialkoxybenzene associated with a linear hydrocarbon group, and any combination thereof. It should be noted that simple diesters in the case of the AOA below are equally used as non-limiting examples of simple diapir ARS.

In one embodiment, ART is a composition promoting the fluidity of the melt. "Compo what icia, promoting the fluidity of the melt in accordance with the use herein is a composition, which, when the operations of the respective process conditions of the present description of the invention, increases the rate of flow of a polymer melt, resulting in the required conditions of the polymerization. Composition, promoting the fluidity of the melt, can be any silane composition suitable for use as the aforementioned ART, simple fluids, alkoxybenzyl, ester, ketone, amide and/or amine.

In one embodiment, the catalyst composition comprises a molar ratio between ARS and ARS, which is less than or equal to 1, or 0.1 to 1.0:1. In one additional embodiment, the molar ratio ARS:ARS is 0.1 to 0.9:1, or 0.2 to 0.5:1. As it was installed, without binding itself to any specific theory, keeping the molar ratio ARS:ARS, smaller or equal to 1.0, the best way allows both ARS to contribute to the properties of the resulting propylene polymer basis.

S-VDE enables the agent that limits activity (AOA). "Agent, limiting the activity in accordance with the usage in this document is a material that reduces the activity of the catalyst when the surface is elevated temperature, namely, in a polymerization reactor under polymerization at a temperature greater than approximately 100°C. the Presence of antioxidant activity the results in self-limiting composition of the catalyst. In accordance with the usage in this document "self-limiting" the catalyst composition is a catalyst composition that exhibits reduced activity at temperatures greater than approximately 100°C. in Other words, the term "self-limiting" refers to the reduction in catalyst activity with increasing reaction temperature above 100°C in comparison with the activity of the catalyst under normal conditions of carrying out polymerization at the reaction temperature, typically less than 80°C. In addition, as a practical standard, you can accept that, if the method of polymerization, such as polymerization in the gas phase in the fluidized bed, passing in the usual process conditions may be interrupted and result in the collapse of a layer with reduced risk in respect of agglomerating the polymer particles, the composition of the catalyst will be called "self-limiting".

In the framework of standardized measures of activity in the polymerization reaction at elevated temperatures used in this document, the CA activity is of alization regulate to compensate for differences in the concentrations of monomer due to temperature. For example, in the case of conditions for polymerization in the liquid phase (slurry or solution) would be to include a correction factor to account for the reduced solubility of propylene in the reaction mixture at elevated temperatures. That is, the catalyst activity "normalize" to compensate for the reduced solubility in comparison with what takes place at lower temperatures, especially when the standard is 67°C. the "Normalized" activity at the temperature T or a_Tdefined as the measured activity or the amount (mass of polymer/weight of catalyst/hour) at a temperature T, multiplied by a correction factor for the concentration of [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 the 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 between the concentration of propylene at 67°C and the concentration of propylene at a temperature T. the Resulting normalized activity (A), adjusted to decrease the concentration of propylene with increasing temperature, can be used to map the activity of the catalyst in the variables the conditions for temperature. Correction factors for conditions used in the polymerization in the liquid phase, the charge below.

As suggested correction factor activity during polymerization increases linearly with increasing concentration of propylene in the used conditions. The correction factor depends on the used solvent or diluent. For example, the correction factors listed above, are common With_6-10aliphatic hydrocarbon mixture (Isopar™E, available at Exxon Chemical Company). In terms of conducting the polymerization in the gas phase solubility of the monomer is usually not important, and in General to account for temperature differences activity is not correct. That is, the activity and the normalized activity will constitute one and the same.

"The ratio of normalized activities" is defined as A_T/A₆₇where a_Tthe submitted is an activity at temperature T, and₆₇represents activity at 67°C. This value can be used as an indicator of changes in the activity depending on the temperature. For example, as demonstrated by the magnitude And₁₀₀/A₆₇0.30 , the activity of the catalyst at 100°C is only 30 percent of the catalyst activity at 67°C. As determined at 100°C ratio And₁₀₀/A₆₇equal to 35% or less, provides the catalyst system, which is self-limiting system.

The AOA can be an aromatic ester or its derivative, aliphatic ester or its derivative, simple fluids, poly(alkalophilicity) ester, and combinations thereof. Non-limiting examples of suitable aromatic esters include_1-10alkalemia or cycloalkyl esters of aromatic monocarboxylic acids. Them suitable substituted derivatives include compounds substituted in the aromatic ring (rings)and ester group one or more substituents containing one or more heteroatoms of groups 14, 15 or 16, in particular oxygen. Examples of such substituents include groups (poly)Olkiluoto simple ether, cycloalkyl simple ether, kilowog simple ether, Arakelova simple EF is RA, Olkiluoto simple tiefer, kilowog simple tiefer, dialkylamino, diarylamino, dialkylamino and trialkylsilanes. A complex ester of aromatic carboxylic acid can be_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 based on the C_1-20(poly)hidrocarburos simple ester 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 one embodiment, an ester of an aromatic monocarboxylic acid represents ethyl(p-ethoxybenzoate).

In one embodiment, the implementation of the AOA represents an aliphatic ester. Aliphatic ester can be₄-C₃₀a complex ester of aliphatic acid, can be complex mono - or poly- (two or more) ether, may be straight or branched chain, may be saturated or unsaturated, and any combination thereof. With₄-C₃₀esters of aliphatic acids may also be substituted by one or more substituents containing a heteroatom of the group is s 14, 15 or 16. Non-limiting examples of suitable₄-C₃₀esters of aliphatic acids include_1-20alkalemia esters of aliphatic C_4-30monocarboxylic acids, With_1-20alkalemia esters of aliphatic C_8-20monocarboxylic acids, With_1-4allyl mono - and diesters of aliphatic C_4-20monocarboxylic acids and dicarboxylic acids, With_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 one additional embodiment, With₄-C₃₀ester of aliphatic acid may be isopropylmyristate and/or di-n-butylsilane.

In one embodiment, the AOA is isopropylmyristate.

In one embodiment, the AOA is a simple fluids. Simple fluids can be diakidoy simple fluids, represented by the following formula

where R¹-R⁴independently from each other represent an alkyl, aryl or aracelio group containing up to 20 carbon atoms, which optionally may contain a heteroatom from group 14, 15, 16 or 17, with the proviso that ¹and R²can be a hydrogen atom. Non-limiting examples of suitable derivatives dialkylated ethers include dimethyl ether, diethyl ether, disutility ether, metaliteracy ether, methylbutylamine ether, 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 one additional embodiment, the derived dialkylamide simple ether is a 2.2-Diisobutyl-1,3-dimethoxypropane.

In one embodiment, the AOA is a poly(alkalophilicity) ester. Non-limiting examples of suitable poly(alkalophilic) ethers include poly(allenglish)mono - or diacetate, poly(allenglish)mono - or demeritte, poly(allenglish)mono - or-delaurenti, poly(allenglish)mono - or-diolaiuti, glycerite(acetate), gliterry complex triavir_2-40aliphatic carboxylic acids and any combination thereof. In one embodiment, poly(alkalinic the left) fragment of poly(alkylenglycol) of ester is a poly(ethylene glycol).

In one embodiment, the molar ratio of the aluminum and the AOA can be 1,4-85:1 or 2.0-50:1 or 4-30:1. In the case of the AOA, which have more than one carboxylate group, all of the carboxylate groups are effective components. For example, sebacina molecule that has two carboxylate functional group, is deemed to include two effective functional molecule.

In one embodiment, the catalyst composition comprises a molar ratio of Al and C-VDE 0.5-25:1, or 1.0 to 20:1 or 1.5 to 15:1, or less than about 6, or less than about 5, or less than about 4.5.

In one embodiment, the molar ratio of Al:C-VDE is 0.5 to 4.0:1. As you can imagine without wanting to be bound to any specific theory, the molar ratio of Al/P-RDE in the range from 0.5:1 to 4.0:1 ensures the presence of a sufficient amount of aluminum to support the completion of the polymerization reaction at normal temperature polymerization. However, at higher temperatures (due to reflux temperature or breach of process parameters, for example) more aluminium-containing substances react with other components of the catalyst. This leads to a deficiency of aluminum, which slows down the passage of the polymerization reaction. The deficit and uminia causes a corresponding decrease in the number of electron donors, complex with aluminum. A pair of free electrons uncomplexed donors poison the catalyst that causes the limitation of the reaction.

In accordance with the use herein of "total art" represents the combined amount (in moles) ARS and ARS. In other words, the total ARS=ARS (mol) +ARS (mol). The number of AOA-VDE improves the ability of the catalyst to provide restraint at elevated temperatures, while the number ARS provides stiffening of the resulting polymer, and the number ARS provides making him melt. The molar ratio between the total ARS and the AOA is 0,43-2,33:1, 0,54-1,85:1 or of 0.67 to 1.5:1. The molar ratio between ARS and total ARS is 0,2-0,5:1, 0,25-0,45:1 or between 0.30 to 0.40:1. As to my surprise suddenly found the applicants, a controlled molar ratio: (1) between ARS and ARS and/or (2) between cumulative ARS and the AOA and/or (3) between ARS and total ARS leads to the synthesis of the resulting polymer with unique properties such as high melt flow and high stiffness in combination with the characteristics of the facilities self-limiting catalyst in the conversion.

In one embodiment, the molar ratio between the total ARS and the AOA the leaves of 0.43 is 2.33:1, and the molar ratio between ARS and total ARS is 0.2 to 0.5:1.

In one embodiment, the catalyst composition comprises a molar ratio between Al and total ARS 1,4-85:1 or 2.0-50:1 or 4.0-30:1.

In one embodiment, the catalyst composition comprises a molar ratio between the total ARS and the AOA, which is less than 1.0. As to the surprise of suddenly was established, keeping the molar ratio between the total ARS and the AOA less than 1.0, greatly improves the convenience of the reactor in circulation.

In one embodiment, S-VDE contains dicyclopentadienyliron (ARS), composition, promoting the fluidity of the melt, (ARS) and isopropylmyristate (AAO). In one additional embodiment, ARS choose from methylcyclohexanecarboxylic, diisobutyldimethoxysilane, di-n-butyldiethanolamine, n-propyltriethoxysilane, benzyltriethylammonium, but-3-initialisieren, 1-(triethoxysilyl)-2-pentene, (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 composition of the catalyst are presented below in table 1.

The present catalyst composition may include two or more versions of the implementation, opissyvayusya in this document.

In one embodiment proposes a method of polymerization. The polymerization method includes the introduction of propylene and optionally at least one other olefin in contact with the catalyst composition in a polymerization reactor during polymerization. The composition of the catalyst can be any catalyst composition, opisyvayuschaya in this document, and includes precatalysts, socialization and mixed the first external electron donor (C-VDE), including the first agent, governing the selectivity, (ARS), the second agent, governing the selectivity, (ARS) and the agent that limits activity (AAO). The method also includes obtaining the propylene polymer basis, characterized by the rate of flow of the melt (P)equal to at least 50 g/10 min as measured in accordance with test method ASTM D 1238-01 at 230°C and a weight of 2.16 kg

In one embodiment, the method includes obtaining the propylene polymer basis, characterized by the value of P greater than 60 g/10 min, or greater than 70 g/10 min, or greater than 80 g/10 min, or greater than 100 g/10 min, or in the range from more than 50 g/10 min to about 1000 g/10 minutes

The method includes the introduction of propylene and optionally at least one other olefin in contact with the catalyst composition in a polymerization reactor. Together with propylene for the reaction with the catalyst and obtain a polymer, copolymer (or fluidised bed of polymer particles in the polymerization reactor can be entered one or more olefinic monomers. Non-limiting 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-dodecene and the like; (C_4-20diole the ins, such as 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB) and Dicyclopentadiene; C_8-40vinylaromatic compounds, including styrene, o-, m - and p-methylsterol, divinylbenzene, vinylbiphenyl, vinylnaphthalene; and halogen-substituted C_8-40vinylaromatic compounds such as chloresterol and forstera.

In one embodiment, the method includes the introduction of propylene in contact with the composition of the catalyst to obtain propylene homopolymer.

In accordance with the usage in this document "conditions for polymerization are the parameters of temperature and pressure in the polymerization reactor, suitable for promotion passage of polymerization between the composition of the catalyst and the olefin with the formation of the desired polymer. The polymerization method may be a method of polymerization in the gas phase, slurry or the extent implemented in one or more than one polymerization reactor. Accordingly, the polymerization reactor can be gas-phase polymerization reactor, liquid-phase polymerization reactor, or a combination of them.

It should be understood that the presence of hydrogen in the polymerization reactor is a component of the conditions of polymerization. During the polymerization, hydrogen explosion is aetsa regulator of the degree of polymerization and has an effect on the molecular weight (and accordingly, the flow velocity of the melt) of the resulting polymer.

In one embodiment, the polymerization is carried out in the form of polymerization in the liquid phase.

In one embodiment, the polymerization is carried out in the form of polymerization in the gas phase. In accordance with the usage in this document polymerization in the gas phase" refers to the passage of the ascending pseudoviruses environment, while pseudozyma environment contains one or more monomers in the presence of a catalyst through a fluidized bed of polymer particles is maintained in fluidized condition by the action pseudoviruses environment. The term "fluidization", "fluid" or "pseudoviruses" refers to the method of introduction into the contact in the system of gas-solid substance, in which a layer of finely ground polymer particles are lifted and agitated by a rising stream of gas. Fluidization occurs in the layer of particles when the flow of the fluid ascending through the voids of the layer of particles, pressure difference and the increment of the resistance of friction greater than the mass of particles. Thus, the "fluidized bed" is a set of polymer particles suspended in a fluid state under the action of a stream pseudoviruses environment. "Pseudozyma environment made the focus of a one or more olefinic gases, optional gaseous media (such as H₂or N₂and optional liquid (such as hydrocarbons), which rise through the gas-phase reactor.

Conventional gas-phase polymerization reactor (or gas-phase reactor) includes a receptacle (i.e., reactor), fluidized bed, the distribution plate, the inlet and outlet pipelines, compressor, refrigerator / gas heat exchanger in the loop and unloading of products. The container includes a reaction zone and a zone of decreasing speed, each of which is located above the distribution plate. The layer is placed in the reaction zone. In one embodiment, pseudozyma environment includes gaseous propylene and at least one other gas, such as olefin and/or gaseous media, such as hydrogen or nitrogen.

In one embodiment, the introduction of the contact is carried out in the feed composition of the catalyst in a polymerization reactor and introducing into the polymerization reactor olefin. In one embodiment, the method includes introducing olefin into contact with socialization. Acetalization can be mixed with the composition of pronatalistic (pre-mix) before the introduction of the composition of pronatalistic in a polymerization reactor. In yet another embodiment, socialization in polymer clay is salony reactor type, 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 one embodiment, the method comprises mixing or other Association WITH the VDE composition of pronatalistic. S-VDE can be notorious with socialization and/or mixed with the composition of pronatalistic (pre-mix) before the introduction of the composition of the catalyst into contact with propylene. In yet another embodiment, S-VDE (or its individual components) can be independently added to the polymerization reactor.

In one embodiment, the method includes maintaining the molar ratio ARS:ARS of 0.1-1.0:1.

In one embodiment, the method is a method of polymerization in the gas phase and involves keeping in gas-phase reactor, the molar ratio between hydrogen and propylene ("H₂/S₃"), less than 0,30, (that is, of 0.30:1) or less than 0,20, or less than 0,18, or less than 0,16, or less than 0,08. It was found that despite the possibility of achieving high melt fluidity in the use of high levels of hydrogen, propylene polymers on the basis of obtained by using a molar ratio of N₂/S₃greater than 0,30,significantly accelerates adverse reactions hydrogenation of propylene in the presence of oxidized carbon steel reactor and reduce the activity of the catalyst. On the other hand, the propylene polymer basis, resulting from the use of this method avoids the presence of excess amounts of catalytic residues, when the molar ratio of N₂/S₃is less than 0.3. In one additional embodiment, the method is a method of polymerization in the gas phase, vpisivaushiesya in being considered concurrently with this application application .... (attorney docket No. 68345), filed February 23, 2009, the contents of which in its entirety by reference is incorporated herein.

In one embodiment, a method of polymerization in the gas phase includes maintaining the partial pressure of hydrogen, less than about 80 lb/inch²(552 kPa), or less than about 71 lbs/inch²(490 kPa), or less than approximately 63 lbs/inch²(434 kPa).

In one embodiment, the method includes the limitation of the method of polymerization in the case of the temperature in the reactor is greater than about 100°C.

In one embodiment, the method includes obtaining a polymer in propylene based in a single polymerization reactor.

In one embodiment, the method includes obtaining the propylene polymer base containing at least CA is approximately 5 ppm of the AOA and characterized by the value of P, greater than about 50 g/10 minutes of the AOA is present in a quantity of at least about 5 ppm, or at least about 10 ppm, or at least about 20 ppm, or at least about 30 ppm, or at least in the range from about 5 ppm to about 150 h/million In one additional embodiment, the AOA is isopropylmyristate (IPM).

In one embodiment, the method includes obtaining the propylene polymer base containing less than about 200 ppm of silicon. In one additional embodiment, the method includes obtaining the propylene polymer base containing less than 200 ppm, or from about 1 ppm to about 200 ppm, or from about 2 ppm to about 100 ppm, dicyclopentadienyliron.

As to my surprise suddenly discovered the applicants, the presence of a mixed external electron donor provides a composition of the catalyst, which is self-limiting and leads to the production of propylene polymers on the basis of high rigidity and high fluidity of the melt, in the same polymerization reactor in the standard conditions of the polymerization. Considered without geraniaceae myself to any specific theory, The AOA increases the convenience in handling the polymerization reactor by preventing the passage of uncontrolled reactions, the formation of polymer layered sediments and/or agglomerating polymer due to excess heat. The presence ARS and ARS makes it possible for the propylene polymer basis, which is characterized by high rigidity (that is, the value of TMF greater than about 170°C)/high fluidity of the melt (i.e., greater than 50 or 60 or 70 or 100 g/10 min), using standard levels of hydrogen content.

In particular, the present method is advantageous manner ensures propylene polymer basis, which is characterized by high rigidity and high fluidity of the melt, without holding a light cracking conventional methods of increasing values of P outside, caused by limitations in the use of hydrogen for the described first high rigid polymer in propylene-based reactor brand. The term "light cracking" (or "cracking") in accordance with the usage in this document relates to a thermal and/or chemical degradation of the polymer with the formation of smaller segments of the polymer chain. Light cracking usually includes the transfer of the polymer (such as polypropylene) in the state of the melt in the presence of freedom is but a radical initiator (such as peroxide) for the decomposition of polypropylene with the formation of smaller segments of the polypropylene chain.

Easy cracking typical of many side effects such as the formation of decomposition products (which often cause odor problems and incompatibility with food), increased cost and reduced stiffness of the polymer. Easy cracking, increasing the fluidity of the melt, still reduces the mass-average molecular weight of the polymer. Light cracking alter the physical and chemical structure of the original polymer. For example, subjected to easy cracking of polypropylene homopolymer will demonstrate the deterioration of physical and/or mechanical properties (i.e., the smaller the modulus of tensile elasticity, the smaller the modulus of elasticity in bending) in comparison with what is to not tucked cracking propylene homopolymer characterized by the same value P.

In one embodiment, the present method results in not subjected to cracking of the polymer propylene basis. The polymer, which is not subjected to cracking"was not subjected to the methods of easy cracking. In other words, not subjected to cracking of the polymer is a polymer that is not subjected to thermal and/or chemical degradation. Not subjected to cracking of the polymer does not detect deterioration in physical and/or mechanical properties, the relative is relevant to molecular weight, (such as the modulus of elasticity in bending and/or mechanical properties tensile), as is the case for polymer subjected to easy cracking, with the same value of P. In addition, not subjected to cracking of the polymer does not detect the presence of decomposition products (which often cause odor problems and incompatibility with food), as is the case for polymer subjected to easy cracking.

In one embodiment, the method includes obtaining the propylene polymer basis, with one or more of the following properties: (i) not subject to cracking propylene homopolymer; (ii) the value of P 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) the level of content material, soluble in xylene, less than 4% (mass.), or less than 3% (mass.), or in the range from about 0.1% (mass.) to less than 2.0% (wt.); (iv) the value of TMF greater than about 165°C., or greater than 170°C; (v) the content of the AOA in the range of at least from about 5 ppm to about 150 ppm; (vi) the amount of oligomers after reactor ("oligomers" are₁₂-C₂₁connection), less than 3000 ppm, or less than 2500 ppm, or nahodyaschiysya the range from about 500 ppm to about 3000 ppm; and/or (vii) the amount of oligomers after the reactor is about 10% or about 20% or about 40% less than the corresponding levels of oligomers in the polymer propylene basis, obtained using the composition of the catalyst, which contains one ARS in the form of a composition, promoting the rigidity (and optional AAO) in similar conditions of polymerization. The term "content of oligomers after reactor in accordance with the usage in this document refers to the level of the content of oligomers in the resulting polymer in propylene based directly after leaving the polymerization reactor. In other words, the content of oligomers after reactor" is the content of oligomers before after polymerization, any of the cleaning procedures, procedures of heating and/or procedures of refinement.

This method of polymerization may include two or more versions of the implementation, opissyvayusya in this document.

In one embodiment, features a propylene polymer basis. The propylene polymer of the base includes at least 5 ppm of the agent, restricting activity. The propylene polymer of the base is characterized by the rate of flow of the melt, the greater the th, than about 50 g/10 minutes of the AOA may be present in a quantity equal to at least 5 ppm, or at least 10 ppm, or at least 20 ppm, or at least about 30 ppm, or in the range of at least from about 5 ppm to about 150 h/million In one additional embodiment, the AOA is isopropylmyristate (IPM).

In one embodiment, the propylene polymer of the base is characterized by a value of P greater than 60 g/10 min, or greater than 70 g/10 min, or greater than 80 g/10 min, or greater than 100 g/10 min, or in the range from more than 50 g/10 min. to about 1000 g/10 minutes

In one embodiment, the propylene polymer is not subjected to cracking.

In one embodiment, the propylene polymer of the base is a propylene homopolymer.

In one embodiment, the propylene polymer of the base includes less than about 200 ppm of silicon, or from about 1 ppm to about 200 ppm, or from about 2 ppm to about 100 ppm of silicon. In one additional embodiment, the propylene polymer of the base comprises from about 1 ppm to about 200 ppm of dicyclopentadienyliron.

In one vari is nThe implementation of the propylene polymer of the base includes property, choose from the following: (i) the level of content material, soluble in xylene of less than about 4% (mass.), to or less than approximately 3% (mass.), or in the range from about 0.1% (mass.) to less than approximately 2.0% (wt.); (ii) the value of TMF greater than about 165°C., or greater than about 170°C; (iii) the amount of oligomers after the reactor is less than about 3000 ppm, or less than about 2500 ppm, or in the range from about 500 ppm to about 3000 ppm; and (iv) any combination of items (i)to(iii).

In one embodiment, the present polymer propylene-based low toxicity or its absence, low content of decomposition products or their absence and/or mild odor or lack of it.

This propylene polymer of the base may include two or more versions of the implementation, opissyvayusya 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 by CRC Press, Inc. in 2003. In addition, any references to the group or groups should relate to the group or groups carried is this periodic table of the elements using the IUPAC system for numbering groups. Unless you will be approved to the contrary, be implied from the context, or be generally recognized state of the art, all parts and percentages will be based on weight. For the purposes of patent practice in the United States the contents of any patent, patent application or publication referenced herein in its entirety by reference is incorporated herein (or by reference hereby incorporated their equivalent version in the US), especially in the description of methods of synthesis, definitions, to the extent that they are not incompatible with any of the definitions presented in this document) and public information modern technology.

The term "comprising" and its derivatives do not purport to exclude the presence of any additional component, step or method, regardless of whether they are described in this document or not. To avoid any doubt, all of the compositions claimed herein through the use of the term "comprising"may include any additional additive, adjuvant or connection, whether polymeric or another, unless stated otherwise. In contrast, the term "essentially consisting of" drop the t from the amount of any subsequent presentation of any other component, stage or method except for those that are not essential from the point of view of usability. The term "consisting of" excludes any component, phase or methods not specifically described or listed. The term "or", unless other specified, refers to the listed members individually and in any combination.

Any numerical range cited herein includes all values from the lower value to the upper value in increments of one unit provided that between any lower value and any of the top value, there is a separation, comprising at least 2 units. By way of example, you can say that in the case of allegations of ingress component quantities or values of composition or physical properties, such as, for example, the number of components of the mixture, the softening temperature, the melt index and the like, in the range from 1 to 100 assumed to be unambiguous enumeration in this description, all individual values, such as 1, 2, 3 and the like, and sub-ranges such as from 1 to 20, from 55 to 70, from 97 to 100, and the like. In the case of values that are less than one, one unit will be considered equal to 0.0001 to 0.001, 0.01 or 0.1, depending on the situation. This is just examples of the CSOs, exactly what is implied, and expressly indicated in this application should be considered all possible combinations of numerical values between the lowest value and highest value. In other words, any numerical range given in this document, includes any value or subrange within the specified range. In accordance with the discussion herein numerical ranges indicated when referring to the melt index, the rate of melt flow and other properties.

The terms "blend" or "polymer blend" in accordance with the usage in this document to mean a mixture of two or more polymers. This mixture may or may not be mixed (not phase-separated on a molecular level). This mixture may or may not be phase-separated. This mixture according to the definition on the methods of transmission electron spectroscopy, light scattering, x-ray scattering and other methods known state of the art, may include or may not include one or more configurations of domains.

The term "composition" in accordance with the use herein includes a mixture of materials that make up the composition, and reaction products and decomposition products formed from the materials to the position.

The term "polymer" refers to a macromolecular compound obtained by polymerization of monomers of the same or different types. "Polymer" includes homopolymers, copolymers, terpolymer (ternary copolymers), interpolymer and the like. The term "interpolymer" means a polymer obtained by polymerization of at least two types of monomers or comonomers. It includes the following but is not limited to: copolymers (commonly referred polymers derived from two different types of monomers or comonomers), terpolymer (commonly referred polymers derived from three different types of monomers or comonomers), terpolymer (commonly referred polymers obtained from four different types of monomers or comonomers), and the like.

The term "interpolymer" in accordance with the use herein means a polymer obtained by polymerization of at least two different types of monomers. Thus, the generic term "interpolymer" includes the term "copolymers", usually used to refer to polymers derived from two different monomers, and polymers derived from more than two different types of monomers.

Terkin "olefinic polymer basis" is a polymer comprising at apolinario the authorized form the main mass percentage of olefin, for example, ethylene or propylene, based on total weight of the polymer. Non-limiting examples of olefin polymers on the basis include polymers based on the ethylene and propylene polymers on the basis.

The term "ethylene polymer basis" in accordance with the usage in this document refers to a polymer that includes a primary mass percentage depolimerization ethylene monomer (based on the total weight of the polymerized monomers), and optionally may include at least one sopolimerizacii comonomer.

The term "propylene polymer basis" in accordance with the usage in this document refers to a polymer that includes a primary mass percentage depolimerization propylene monomer (based on the total weight of the polymerized monomers), and optionally may include at least one sopolimerizacii comonomer.

The term "alkyl" in accordance with the use herein refers to a branched or unbranched, saturated or unsaturated acyclic hydrocarbon radical. Non-limiting examples of suitable alkyl radicals include, for example, methyl, ethyl, n-propyl, isopropyl, 2-propenyl (or allyl), vinyl, n-butyl, tert-butyl, isobutyl or 2-methylpropyl) and the like. Alki the s contain from 1 to 20 carbon atoms.

The term "substituted alkyl" in accordance with the use in this document only applies to that described for the alkyl, in which one or more hydrogen atoms associated with any carbon atom of the alkyl is replaced by another group such as halogen, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, heteroseksualci, substituted heteroseksualci, halogen, halogenated, hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, and combinations thereof. Suitable substituted alkali include, for example, benzyl, trifluoromethyl and the like.

The term "aryl" in accordance with the usage in this document refers to the aromatic Deputy, which can be a single aromatic ring or multiple aromatic rings that are condensed with each other, covalently bound or linked to a common group such as a methylene or ethylene fragment. The aromatic ring (ring) may include, without limitation, phenyl, naphthyl, anthracene and biphenyl. Arily contain from 1 to 20 carbon atoms.

TEST METHODS

The modulus of elasticity in bending is determined in accordance with ASTM D790-00.

The rate of melt flow (P) is measured in accordance with test method ASTM D 1238-01 at 230°C and a weight of 2.16 kg for propylene polymers on the basis.

The level of content material which a, soluble in xylene, (RK) is measured using 1H NMR as described in U.S. patent No. 5539309, the content of which in its entirety by reference is incorporated herein.

The temperature of the end of melting (TMF) is the melting temperature of the most perfect crystal in the sample and is a measure of isotacticity and own crystallochemistry polymer. The test is carried out using differential scanning calorimeter (TA Q100. The sample is heated from 0°C to 240°C at 80°C/min, cooled down with the same speed to 0°C, then heated again with the same speed of up to 150°C, maintained at 150°C for 5 minutes and heated from 150°C to 180°C at 1.25°C/min, the Value of TMF is determined by this last cycle in the calculation of the beginning of the baseline at the end of the heating curve.

Test method:

(1) instrument Calibration when using high purity indium as standard.

(2) the Constant blowing head/cell device at a constant nitrogen flow of 50 ml/min

(3) obtaining a sample:

Direct pressing of 1.5 g of powdered sample using the direct extrusion 30-G302H-18-CX Wabash (30 tons): (a) contacting the heated mixture at 230°C for 2 minutes; (b) pressing the sample at the same temperature and pressure and 20 tons for 1 minute; (C) cooling the sample to 45°F (7.2°C) and holding for 2 minutes under a pressure of 20 tons; (d) cutting the plate into 4 pieces approximately identical size, put them in a stack with each other and repeating steps (a)-(C) to homogenize the sample.

(4) Using a fragment of the sample (preferably in the range of from 5 to 8 mg) of the plate of the sample and sealing it in standard aluminum cell for samples. Placing a sealed cuvette containing the sample, at the Department for sample head/cell device and placing an empty sealed pan in the Department for the control sample.

(5) Dimension:

(i) Accumulation of data: disabled.

(ii) Linear change in 80,00°C/min to 240,00°C.

(iii) Isothermal holding for 1,00 minutes

(iv) Linear change in 80,00°C/min to 0.00°C.

(v) Isothermal holding for 1,00 minutes

(vi) a Linear change in 80,00°C/min to 150.00°C.

(vii) Isothermal holding for 5,00 minutes

(viii) the Accumulation of data: enabled.

(ix) Linear change at 1.25°C/min to 180,00°C.

(x) the Completion of the method.

(6) Calculation: the value of T_MFdetermined by the intersection of two lines. Drawing one line from the baseline at high temperature. Drawing another line on the deviation of the curve near the end of the curve on the high temperature side is E.

Test method for determining levels of oligomers: the content of oligomers measured in the extraction of the polymer sample during the night in solution in chloroform containing n-hexadecane as an internal standard. An aliquot of the extract is shaken with methanol, and then filtered to remove any precipitated high molecular weight polypropylene and solid particles. The filtered liquid is introduced into the capillary chromatographic column of fused silica using the introduction of the cold sample directly into the column. The relative amount of extracted components calculated based on the mass of the extracted polymer.

By way of example and not limitation will now presents examples of the present description of the invention.

EXAMPLES

Example 1

(1) Precatalysts:

A. Precatalysts V10B is a commercial catalyst SHAC™ 320 containing 2,52% (mass.) Ti and 10,34% (mass.) diisobutylphthalate (DiBP).

Century Precatalysts 1910-29-2 receive in accordance with the method for catalyst 4949-25-1 in the provisional patent application U.S. No. 61/141902, filed December 31, 2008, the contents of which in its entirety by reference is incorporated herein. Precatalysts 1910-29-2 contains 3,61% (mass.) Ti and 14.85% (mass.) 3-METI the-5-tert-butyl-1,2-phenylendiamine.

(2) Components of the external electron donor:

592420: (triethoxysilyl)cyclohexane.

BPIQ - bis(perhydrosqualene)dimethoxysilane.

Catepe: 1 ethoxy-2-n-phenoxybenzoyl.

D (or a donor (D): dicyclopentadienyliron.

DAB 5: 1 ethoxy-2-(6-(2-ethoxyphenoxy)hexyloxy)benzene.

DiBDES: diisobutyldimethoxysilane.

DiPDMS - diisobutyldimethoxysilane.

DMDMS - dimethyldiethoxysilane.

DnBDMS: di-n-butyldimethylsilyl.

IPM: isopropylmyristate.

MChDES: methylcyclohexanecarboxylic.

MChDMS - methylcyclohexanecarboxylic.

PEEB - ethyl(p-ethoxybenzoate).

PTES - n-propyltriethoxysilane.

PTES: n-propyltriethoxysilane.

S-191 - ester derived from PoE (15) and fatty acids of coconut oil.

SIB0971.0: benzyltriethylammonium.

SIB1928.0: butyltrichlorosilane.

TEOS: tetraethoxysilane.

(3) Polymerization:

A. Liquid-phase polymerization is carried out in liquid propylene in an autoclave with a volume of 1 gallon (3,79 DM³). After conditioning in the reactor load 1375 g of propylene and the target amount of hydrogen and the temperature is brought to 62°C. Component (s) an external electron donor added to a solution of triethylaluminum in isooctane concentration of 0.27 mol/l and the suspension of catalyst in mineral oil with a concentration of 5.0% (wt.) (as indicated in the following tables with the data and conduct the seat reservation stirring at ambient temperature for 20 minutes before introduction into the reactor to initiate polymerization. Pre-mixed components of the catalyst introduced into the reactor by a stream together with isooctane when using high-pressure pump for introduction of catalyst. After heat temperature controlled withstand equal to 67°C. the Total curing time is 1 hour.

The properties of the polymer, including the level of content material, soluble in xylene, (RK), the content of oligomers and the value of T_MFdepend on the fluidity of the melt. Precatalysts V10B, using as ARS donor D, is used as the baseline. The results are presented in table 2. The data in table 2 are used to create standard curves (figures 1 and 2) and obtain equations for the calculation of the "standard" values for comparison with the polymers obtained when using catalyst compositions containing S-VDE.

Example 2

(1) Precatalysts: Use the commercial catalyst SHAC™ 320 (2,59% Ti) and DiBP. The suspension of catalyst was prepared in toluene with a concentration of 0,247 mg/ml. All ARS and the AOA diluted to 0.005 mol/l in Isopar E™ except S-191, which is dissolved in toluene before you put the eat in WIP. TEAL get in Isopar E™ and used in the form of solutions with concentrations or 0.02, or 0.1 mol/L.

(2) Polymerization: Blown parallel polymerization reactor (PPR) is heated to 50°C and in each reactor type DEAL and make-up solvent Isopar E™, followed by addition of N₂to achieve a stable pressure of 5 lb/in²(wt.) (34,5 kPa (psig). The reactor is heated to a predetermined temperature (67, 100, or 115°C). Propylene add up to 100 lb/in²(wt.) (689 kPa (psig) and provide stabilization for 10 minutes In each reactor type APC or a mixture ARS, ARS and the AOA and 500 μl of acceptor unreacted substances in the solvent Isopar E™ immediately following addition of the catalyst (275 μl) and 500 μl of acceptor unreacted substances in the solvent Isopar E™. Reaction quenched WITH₂after 60 minutes or when the maximum relative degree of conversion of 110.

(3) Calculation: Calculate the concentration of propylene in Isopar E™ in WIP at different temperatures. The following table 8 summarizes the normalized ratio of activities and illustrates the property of limiting the present catalyst compositions. For DMDMS/MChDMS 50/50 ratio between the normalized activity of the catalyst at 100°C and activity at 67°With the/A67 is 43% (table 8). In the keeping of the quantitative ratio of DMDMS/MChDMS equal to 1/1, while replacing 95% of the mixture donors connection REEF system DMDMS/MChDMS/PEEB 2,5/2,5/95 demonstrated the value And/A67 at 100°C 21%. This means that the catalyst is characterized by a significantly lower activity compared to the activity at 67°C after adding REEF. That is, the catalyst is more "self-limiting". The same trend holds true also for the activity at 115°C.

The property limiting the present composition of the catalyst has also been observed for other systems ARS/ARS/AAO formed from alkylalkoxysilane, such as DiPDMS/TEOS, DCPDMS/TEOS and DCPDMS/MChDMS in the presence of the AOA, such as REEF. In the case of replacement of REEF derived poly(alkylenglycol) of ester, such as S-191, the effect of self-restraint will be strong (table 8) even with an increased molar ratio of Al/P-RDE. Similar results are observed in the case of the AOA in the form of isopropylmyristate (IPM).

The composition of catalysts containing S-VDE, vpisivaushiesya in this document represent samagra icehouses system while preserving the benefits of several ARS. The presence of the composition, promoting the fluidity of the melt, such as ARS, increases the value P of the resulting polymer. The catalyst composition containing S-VDE, provide for the production of polymers, characterized by rigidity, essentially identical, or identical to the stiffness of the polymer, is achievable as a result of use of the composition of the catalyst, soderjasimi composition, promoting rigidity (such as dicyclopentadienyliron) as the only external electron donor. The presence of the composition, promoting rigidity, such as ARS, results in a polymer which is characterized by high rigidity, as demonstrated by the example values of T_MFin tables 2-7.

The levels of total oligomers to polymers obtained using this catalyst composition, will be considerably reduced in comparison with the level of content of the oligomer in the case of use of the composition, the promoting rigidity (such as dicyclopentadienyliron) as the only external donor at the same melt flow.

These polymers are not subject to easy cracking and is characterized by high fluidity of the melt, high stiffness, and low levels of oligomers, low toxicity or OTS is tsteam and/or low levels of degradation products or their absence.

How exactly it is supposed, the present invention is not limited to variants of implementation and illustrations included in this document, but include modified forms of these embodiments, including part of the embodiments and combinations of elements of different embodiments presented in volume following further claims.

1. The composition of the catalyst, including: the composition of pronatalistic Ziegler-Natta containing titanium, magnesium and the internal electron donor containing at least two oxygen-containing functional groups with oxygen-containing functional groups separated by at least one saturated With₂-C₁₀hydrocarbon chain, which optionally may contain a heteroatom; alyuminiiorganicheskikh connection as socializaton; and a mixed external electron donor (C-VDE), including the agent, limiting activity (AOA), the first agent, governing the selectivity (ARS), which contains an alkoxysilane, and a second agent, governing the selectivity (ARS)selected from the group consisting of alkoxysilane, simple diapir and dialkoxybenzene, and the molar ratio ARS:ARS is from 0.1:1 to 1.0:1, the molar ratio of the total ARS to the AOA is less than 1.0, and this antioxidant activity is beraut from the group consisting of aromatic ether complex or its derivative, aliphatic ether complex or its derivative, simple diapir, poly(alkylenglycol) of ester and combinations thereof.

2. The composition of the catalyst according to claim 1, where ART includes a compound selected from the group consisting of dimethoxysilane, dimethoxysilane having at least one secondary alkyl group, dimethoxysilane having a secondary amino group directly related to the silicon atom, and combinations thereof.

3. The composition of the catalyst according to claim 1, where ARC selected from the group consisting of diethoxyethane, triethoxysilane, tetraethoxysilane, triethoxysilane, simple diapir, dialkoxybenzene, dimethoxysilane having two linear alkyl groups, dimethoxysilane having two alkeneamine group, and combinations thereof.

4. The composition of the catalyst according to claim 1, where the AOA is chosen from the group consisting of aromatic ether complex or its derivative, simple diapir, poly(alkylenglycol) of ester and combinations thereof.

5. The composition of the catalyst according to claim 1, where ARC selected from the group consisting of methylcyclohexanecarboxylic, diisobutyldimethoxysilane, n-propyltriethoxysilane, tetraethoxysilane, di-n-butyldiethanolamine, benzyltriethylammonium, but-3-initialisieren, 1-(triethoxysilyl)-2-pentene, (retaxation)cyclohexane, and combinations thereof.

6. The composition of the catalyst according to claim 1, where the AOA includes isopropylmyristate.

7. The composition of the catalyst according to claim 1, where ART contains dicyclopentadienyliron and ARC selected from the group consisting of methylcyclohexylamine, di-n-butyldiethanolamine, n-propyltriethoxysilane, benzyltriethylammonium and (triethoxysilyl)cyclohexane.

8. The composition of the catalyst according to claim 1, where ART contains dicyclopentadienyliron and ARC contains 1 ethoxy-2-n-phenoxybenzoyl.

9. The composition of the catalyst according to claim 1, where the AOA include_1-4alkalemia esters of aliphatic C_8-20monocarboxylic acids.

10. The composition of the catalyst according to claim 1, where ARC selected from the group consisting of dicyclopentadienyliron and diisobutyldimethoxysilane and ARC selected from the group consisting of vinyltriethoxysilane, dimethyldiethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane and tetraethoxysilane.