Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/06—Propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/06—Propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
  • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages

Definitions

• the present invention relates to a method for producing a propylene polymer material using a Ziegler-Natta catalyst and an organozinc compound, and to the propylene polymer material.
• Propylene polymer materials have excellent rigidity, tensile strength, heat resistance, chemical resistance, optical properties, processability, etc., and have low specific gravity, so they are used in home appliance parts, packaging materials, daily goods, automobile parts, etc. It is used as a material and has a wide variety of uses.
• ZN catalysts for olefin polymerization
• ZN catalysts Ziegler-Natta type catalysts for olefin polymerization
• IUPAC Nomenclature of Inorganic Chemistry, 1989
• transition metal compounds of groups 1 to 6 of the periodic table (IUPAC) metal compounds of groups 1 to 3 of the periodic table (IUPAC)
• IUPAC optionally compounds of group 13 of the periodic table
• the ZN catalyst may also contain further catalyst components such as co-catalysts and/or external donors.
• Patent Document 1 describes an olefin polymer produced using a Ziegler-Natta catalyst and a catalyst containing an organic zinc compound.
• the produced olefin polymers are applied to various uses, but in order to be used suitably in molding processes that require low viscosity and high fluidity, it is preferable that the molecular weight distribution is small. Contributes to stability of nozzle pressure and uniformity of filament fineness in the spinning process. In addition, polymer components with very low molecular weights may cause smoke and odor during processing, and may reduce the strength of molded products. Small polymers are useful. Furthermore, it is preferable that the color be close to white so that it can be used for various purposes. However, Patent Document 1 does not mention the molecular weight distribution and color of the olefin polymer.
• the problem to be solved by the present invention is to provide a propylene polymer material with a small molecular weight distribution that can be suitably used in molding processes that require low viscosity and high fluidity, and that can be used in various applications.
• the object of the invention is to provide a propylene polymer material that is near white in color and can be used.
• the present invention is as follows.
• a method for producing a propylene polymer material comprising a continuous withdrawal step of continuously withdrawing a portion of the propylene polymer material obtained in the reactor from the reactor.
• the propylene polymer material is a copolymer obtained by copolymerizing an olefin other than propylene with propylene, The content of olefin units other than propylene is 0.01 to 10 wt% when the copolymer is 100 wt%.
• the propylene polymer material produced under specific conditions using a Ziegler-Natta catalyst and an organozinc compound has a small molecular weight distribution. Therefore, it can be suitably used in molding processes that require low viscosity and high fluidity. Furthermore, since the color is close to white, it can be used for a variety of purposes.
• the manufacturing method of the present invention is as follows: a continuous supply step of continuously supplying propylene, a solid catalyst component for olefin polymerization, an organoaluminum compound, and an organozinc compound to a reactor; 1. A method for producing a propylene polymer material, comprising a continuous withdrawal step of continuously withdrawing a portion of the propylene polymer material obtained in the reactor from the reactor.
• the solid catalyst component for olefin polymerization used in the production method of the present invention preferably contains titanium atoms and magnesium atoms.
• the following methods (1) to (5) can be exemplified: (1) A method of bringing a halogenated magnesium compound and a titanium compound into contact; (2) A method of bringing a halogenated magnesium compound, an internal electron donor, and a titanium compound into contact; (3) A method of dissolving a halogenated magnesium compound and a titanium compound in an electron-donating solvent to obtain a solution, and then impregnating a carrier material with the solution; (4) A method of bringing a dialkoxymagnesium compound, a halogenated titanium compound, and an internal electron donor into contact; (5) A method of contacting a solid component containing a magnesium atom, a titanium atom, and a hydrocarbon
• the solid catalyst component obtained by the method (4) or (5) is preferable, and the group consisting of a monoester compound, a dicarboxylic acid ester compound, a diol diester compound, a diether compound, or a ⁇ -alkoxy ester compound as an internal electron donor is preferable. More preferably, it is a solid catalyst component containing at least one compound selected from the following. Examples of monoester compounds, dicarboxylic acid ester compounds, diol diester compounds, diether compounds, and ⁇ -alkoxy ester compounds include compounds described in patent documents (Japanese Patent Application No. 2018-531923), and combinations of two or more of these. can.
• Examples of the above-mentioned solid catalyst components for olefin polymerization include JP-A-63-142008, JP-A-4-227604, JP-A-5-339319, JP-A-6-179720, and JP-A-Hei 7-1. 116252, JP 8-134124, JP 9-31119, JP 11-228628, JP 11-80234, JP 11-322833, Japanese Patent Application 2018-531923, Examples include solid catalyst components for olefin polymerization described in JP-A-2021-161216, JP-A-2022-31142, and the like. When using this solid catalyst component for olefin polymerization, it is preferable to use an organoaluminum compound in combination, and if necessary, an external electron donating compound is used in combination.
• Organoaluminum compounds used in the production method of the present invention include trialkylaluminums such as trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; diethylaluminium monochloride; , alkyl aluminum halides such as diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, and ethyl aluminum dichloride; alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; aluminum alkoxides such as diethylaluminum ethoxide and diethylaluminium phenoxide; Examples include alumoxanes such as methylalumoxane, ethylalumoxane, isobuty
• an external electron donating compound (external electron donor) can also be continuously supplied to the reactor as an optional component.
• the external electron donor compound is a monoester compound, a dicarboxylic acid ester compound, a diol diester compound, a diether compound, a ⁇ -alkoxy ester compound, or a silicon compound represented by the following formula [7] as an internal electron donor.
• R 7 represents a hydrogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, or a group containing a hetero atom, and when there is a plurality of R 7 s, they are the same or different
• R 8 is a group containing 1 to 20 carbon atoms
• It represents a hydrocarbyl group, and when there is a plurality of R 8 's, they are the same or different
• r represents an integer from 0 to 3
• r is preferably 1 or 2, more preferably 2.
• hydrocarbyl group having 1 to 20 carbon atoms in R 7 and R 8 a linear alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, and pentyl group; isopropyl group, sec.
• alkyl groups having 3 to 20 carbon atoms such as butyl group, tert-butyl group, and tert-amyl group; cycloalkyl groups having 3 to 20 carbon atoms such as cyclopentyl group and cyclohexyl group; cyclopentenyl group Examples include cycloalkenyl groups having 3 to 20 carbon atoms such as cycloalkenyl groups having 3 to 20 carbon atoms; and aryl groups having 6 to 20 carbon atoms such as phenyl and tolyl groups.
• R 7 is preferably a methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, tert-butyl group, tert-amyl group, cyclopentyl group, cyclohexyl group, phenyl group, diethylamino group, More preferred are methyl group, ethyl group, n-propyl group, tert-butyl group, cyclohexyl group, and diethylamino group.
• R 8 is preferably a methyl group or an ethyl group, more preferably a methyl group.
• Groups containing an oxygen atom such as furyl group, pyranyl group, and perhydrofuryl group; dimethylamino group, methylethylamino group, diethylamino group, ethyl-n-propylamino group as a heteroatom-containing group for R 7 ; group, di-n-propylamino group, pyrrolyl group, pyridyl group, pyrrolidinyl group, piperidyl group, perhydroindolyl group, perhydroisoindolyl group, perhydroquinolyl group, perhydroisoquinolyl group, perhydrocarba
• groups containing a nitrogen atom such as a zolyl group and a perhydroacridinyl group
• groups containing a sulfur atom such as a thienyl group
• groups containing a phosphorus atom such as furyl group, pyranyl group, and perhydrofuryl group
• the hetero atom is a group capable of direct chemical bonding with the silicon atom of the silicon compound, more preferably a dimethylamino group, methylethylamino group, diethylamino group, ethyl-n-propylamino group or di-n- It is a propylamino group.
• the organic zinc compounds used in the production method of the present invention include dialkylzincs such as dimethylzinc, diethylzinc, di-n-propylzinc, di-n-butylzinc, diisobutylzinc, and di-n-hexylzinc; Examples may include diarylzincs such as diphenylzinc and dinaphthylzinc; bis(cyclopentadienyl)zinc; and dialkenylzincs such as diallylzinc.
• dialkylzincs such as dimethylzinc, diethylzinc, di-n-propylzinc, di-n-butylzinc, diisobutylzinc, and di-n-hexylzinc
• diarylzincs such as diphenylzinc and dinaphthylzinc
• bis(cyclopentadienyl)zinc bis(cyclopentadienyl)zinc
• dialkylzinc is preferable, dimethylzinc, diethylzinc, di-n-propylzinc, di-n-butylzinc, diisobutylzinc or di-n-hexylzinc is more preferable, still more preferably dimethylzinc or Diethylzinc is particularly preferred, and diethylzinc is particularly preferred.
• olefins can be used as monomers, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1- Linear olefins such as heptene, 1-octene, and 1-decene; branched olefins such as 3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene; vinyl Examples include alicyclic olefins such as cyclohexane; and combinations of two or more thereof.
• the feed to the reactor must be essentially free of catalyst-deactivating poisons.
• poisons include trace oxygenates such as water, fatty acids, alcohols, ketones and aldehydes.
• Such poisons are removed from the feed to the reactor using standard purification procedures, including, but not limited to, molecular sieve beds, alumina beds, and oxygen removal catalysts for feed purification. .
• propylene and monomers other than the above-mentioned propylene monomers derived from fossil resources, monomers derived from plants, chemically recycled monomers, etc. can be used, and two or more of these may be used in combination.
• Fossil resource-derived monomers are derived from carbon as underground resources such as oil, coal, and natural gas, and generally contain almost no carbon-14 (14C).
• Examples of methods for producing monomers derived from fossil resources include known methods, such as methods for producing olefins by cracking petroleum-derived naphtha, ethane, etc., dehydrogenating ethane, propane, etc.
• Plant-derived monomers are derived from carbon that circulates on the earth's surface as plants and animals, and generally contain a certain percentage of carbon-14 (14C).
• Methods for producing plant-derived monomers include known methods such as cracking of bio-naphtha, vegetable oil, animal oil, etc., dehydrogenation of bio-propane, etc., and alcohol production from fermented products such as sugar extracted from plant materials such as sugar cane and corn.
• a method in which ethylene obtained from plant-derived ethanol and n-butene undergo a metathesis reaction (WO2007/055361 etc.) can be mentioned.
• Chemical recycling monomers are derived from carbon generated from the decomposition and combustion of waste, and their carbon-14 (14C) content varies depending on the waste. Chemical recycling monomers can be produced using known methods, such as thermal decomposition of waste plastics (Top Publication No. 2017-512246, etc.), cracking of waste vegetable oil, waste animal oil, etc. (Top Publication No. 2018-522087, etc.), Methods of gasifying, converting alcohol, and dehydrating wastes such as kitchen garbage, biomass waste, food waste, waste oil, waste wood, paper waste, and waste plastics (Japanese Patent Application Laid-open No. 2019-167424, WO2021/006245, etc.) are cited as examples. It will be done.
• the propylene polymeric materials produced in the present invention are preferably propylene homopolymers or propylene-ethylene copolymers, propylene-1-butene copolymers, and propylene-1-hexene copolymers. , a copolymer of propylene and other olefins.
• the intrinsic viscosity of the polymer is usually 0.5 to 15 dl/g, preferably 0.8 to 10 dl/g.
• the content of other olefin units in the copolymer is 0.01 to 10 wt%, preferably 0.1 to 8 wt%, based on 100 wt% of the copolymer.
• the reactor used in the continuous supply step and continuous withdrawal step of the production method of the present invention is a reactor in which internal homogeneity is maintained by stirring, etc. in the liquid phase, and gas flow, etc. in the gas phase.
• the reactor may have a fractional structure in its internal polymerization region, it is preferable that each fractional structure is as homogeneous as possible.
• a single reactor may be used, it is also possible to connect a plurality of reactors. When connecting a plurality of reactors, it is preferable to connect them in series.
• At least propylene, a solid catalyst component for olefin polymerization, and an organoaluminum compound are supplied to the most upstream reactor, and the reactor to which the organozinc compound is supplied is It may also be fed continuously as polymer content from the previous reactor. Furthermore, although the organozinc compound is supplied to at least one reactor, it may be supplied to a plurality of reactors. In the production method of the present invention, it is preferable that in the continuous supply step, the organoaluminum compound and the organozinc compound are continuously supplied to the reactor using separate lines.
• a propylene polymer material is obtained through a step (polymerization step) of polymerizing propylene continuously supplied in a reactor in a continuous supply step; Propylene polymer material is continuously removed from the reactor.
• a portion of the propylene, solid catalyst component for olefin polymerization, organoaluminum compound, and organozinc compound supplied in the continuous supply step is also taken out, and these concentrations in the reactor are maintained at a constant level. kept in range. In particular, it is considered effective to maintain the concentration of the organozinc compound consumed during the polymerization reaction within a certain range in order to stably obtain the desired propylene polymer material with a small molecular weight distribution.
• the supply rate of each component supplied in the continuous supply process and the withdrawal rate in the continuous withdrawal process can be varied within a range that allows the concentration of each component in the reactor to be kept constant.
• the concentration of each component in the reactor is preferably maintained within ⁇ 30% of the target concentration. More preferably, it is within ⁇ 10%.
• at least a portion of the continuous supply step and at least a portion of the continuous withdrawal step are performed simultaneously.
• the feed rate of the organozinc compound in the continuous supply step with respect to the production rate of the propylene polymer material in the continuous take-out step is 20 to 1000 (mmol-Zn/kg-PP), and 20 to 500 (mmol-Zn/kg-PP). Zn/kg-PP) is more preferable.
• the feed rate of the organozinc compound relative to the feed rate of the organoaluminum compound is preferably 1.1 to 15 (mol-Zn/mol-Al), and preferably 1.2 to 10 (mol-Zn). /mol-Al) is more preferable.
• the feed rate of the organoaluminum compound in the continuous supply step with respect to the production rate of the propylene polymer material in the continuous take-out step is 1 to 30 (mmol-Al/kg-PP), and preferably 2 to 30 (mmol-Al/kg-PP). Al/kg-PP) is more preferable.
• the continuous supply step it is preferable to further continuously supply hydrogen gas to the reactor.
• the number of polymerization steps in the production method of the present invention is 1 or 2 or more.
• the type and amount of monomer polymerized in each step and the polymerization conditions of each step may be different from each other, but propylene is polymerized in at least one step.
• the olefin polymer discharged from the final step is essentially a mixture of the polymers produced in each step.
• Contacting the organozinc compound, the solid catalyst component, the organoaluminium compound, and the external electron donating compound can be carried out by diluting these compounds or components with a solvent or without using a solvent, in the reactor or outside the reactor. It will be done.
• the order in which these compounds and components are brought into contact is not particularly limited, but in the exemplified method, the organoaluminum compound and the external electron donating compound are supplied to the reactor, and then the organozinc compound and the solid catalyst component are brought into contact with each other.
• the feeding to the reactor is preferably carried out in a moisture-free manner under an inert gas such as nitrogen or argon.
• the amount of the organoaluminum compound used is usually 1 to 1000 mol, preferably 5 to 1000 mol, per 1 mol of titanium atom in the solid catalyst component. ⁇ 600 moles.
• the amount of external electron donating compound used in the main polymerization is usually 0.1 to 2000 mol, preferably 0.3 to 1000 mol, and more Preferably, it is 0.5 to 800 mol, usually 0.001 to 5 mol, preferably 0.005 to 3 mol, more preferably 0.01 to 1 mol, based on the organoaluminum compound. .
• the polymerization temperature in the main polymerization is usually -30 to 300°C, preferably 20 to 180°C, and more preferably 40 to 100°C.
• the polymerization pressure is usually normal pressure to 10 MPa, preferably 200 kPa to 5 MPa.
• the polymerization time is usually 0.2 to 10 hours. Preferably it is 0.5 to 6 hours. When multiple reactors are used, the average residence time in each reactor is 0.05 to 5 hours, preferably 0.1 to 3 hours.
• Examples of the polymerization reactor include a loop reactor, a continuous stirred tank reactor, a fluidized bed reactor, and a spouted bed reactor.
• This polymerization can be carried out by slurry or solution polymerization using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, or octane, by bulk polymerization using an olefin that is liquid at the polymerization temperature, or by gas polymerization.
• an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, or octane
• a phase polymerization method or a method combining two or more of these methods it is preferable to include at least a bulk polymerization method.
• it is carried out in a batch method, at least a continuous method, or a combination thereof.
• a plurality of polymerization reactors arranged in series with mutually different polymerization conditions may be used. Polymerization conditions may be varied continuously within one reactor.
• a chain transfer agent such as hydrogen may be used to control the molecular weight of the propylene polymer material obtained in the main polymerization.
• a prepolymerized solid catalyst component described below may be used instead of the solid catalyst component in order to improve the particle properties of the resulting propylene polymer material powder.
• the organoaluminum compound in the main polymerization is not essential.
• preliminary polymerization may be performed by a known method before carrying out the main polymerization.
• Known prepolymerization methods include, for example, supplying a small amount of olefin (same or different from the olefin for main polymerization) in the presence of a solid catalyst component and an organoaluminum compound, and polymerizing in a slurry state using a solvent.
• olefin unsame or different from the olefin for main polymerization
• a solid catalyst component and an organoaluminum compound an organoaluminum compound
• Inert hydrocarbon solvents such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, benzene, xylene, and toluene are used for slurrying.
• I can give an example.
• Part or all of the solvent can be replaced with a liquid olefin.
• Prepolymerization can also be carried out in the presence of a viscous material such as an olefin wax to obtain a prepolymerized catalyst that is stable during storage and handling. Further, the embodiment of the prepolymerization is not particularly limited, and it can be carried out by any of a batch method, a semi-batch method, and a continuous method.
• the amount of organoaluminum compound used in prepolymerization is usually 0.5 to 700 mol, preferably 0.8 to 500 mol, more preferably 1 to 200 mol per mol of titanium atom in the solid catalyst component. It is.
• the amount of olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, and more preferably 0.1 to 200 g per 1 g of solid catalyst component.
• the slurry concentration in prepolymerization is preferably 1 to 500 g-solid catalyst component/liter-solvent, more preferably 3-300 g-solid catalyst component/liter-solvent.
• the prepolymerization temperature is preferably -20 to 100°C, more preferably 0 to 80°C.
• the polymerization time of the preliminary polymerization is usually 30 seconds to 15 hours.
• the partial pressure of the olefin in the gas phase during prepolymerization is preferably 1 kPa to 2 MPa, more preferably 10 kPa to 1 MPa, but this does not apply to olefins that are liquid at the pressure and temperature of prepolymerization. .
• a method of supplying a solid catalyst component, an organoaluminum compound, and an olefin to a prepolymerization tank is as follows: (1) After bringing the solid catalyst component and the organoaluminum compound into contact, the contact material and the olefin are supplied. and (2) a method of bringing the solid catalyst component into contact with the olefin and then supplying the contact material with the organoaluminum compound.
• methods for supplying the olefin include (1) a method of sequentially supplying the olefin so as to maintain a predetermined pressure in the prepolymerization tank, and (2) a method of supplying the entire predetermined amount of olefin first. can.
• Chain transfer agents such as hydrogen may be added to control the molecular weight of the prepolymerized olefin polymer.
• an organozinc compound or an external electron donating compound may be used for the prepolymerization.
• the amount of the external electron donating compound to be used is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, more preferably 0.01 to 400 mol, more preferably 0.02 to 200 mol, per 1 mol of titanium atom contained in the solid catalyst component.
• the amount is usually 0.003 to 5 mol, preferably 0.005 to 3 mol, and more preferably 0.01 to 2 mol, based on the organoaluminum compound.
• methods for supplying the external electron donating compound to the prepolymerization tank include (1) a method of supplying it separately from the organoaluminum compound, and (2) a method of feeding the external electron donor compound and the organoaluminum compound in contact with each other.
• a method of supplying the information can be exemplified.
• preactivation may be performed by known methods. Preactivation can be carried out instead of or before prepolymerization.
• Known preactivation methods include, for example, a method of contacting a solid catalyst component with an organoaluminum in a solvent in the absence of an olefin, and examples of the solvent used include propane, butane, isobutane, pentane, isopentane, Inert hydrocarbon solvents such as hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, benzene, xylene and toluene may be mentioned.
• an organozinc compound or an external electron donating compound may be used for preactivation.
• Preactivated catalysts exhibit, in particular, a significantly lower tendency to form deposits, the degree of preactivation is set in a stable manner for relatively long storage times, and reproducible production conditions are set over long periods of time. It can be so.
• the resulting preactivated catalyst can be metered into a continuously operated stirred reactor.
• Preactivation can also be carried out in the presence of a viscous material such as an olefin wax to obtain a preactivated catalyst that is stable during storage and handling.
• the embodiment of preactivation is not particularly limited, and it can be carried out by any of a batch method, a semi-batch method, and a continuous method.
• the propylene polymer material obtained in the polymerization process of the present invention has an organometallic-containing end group containing organozinc at at least a portion of the end of its polymer chain.
• organometallic-containing terminal group In the case of a linear polymer chain, it usually has an organometallic-containing terminal group only at one end.
• Organometallic-containing end groups are generally highly reactive, for example in any non-polymerizable reaction step with active proton compounds such as water, alcohols, carboxylic acids, or reactive gas compounds such as oxygen or carbon dioxide. can be stabilized.
• Examples of the terminal group after stabilization include a hydroxyl group and a carboxyl group.
• the propylene polymer material of the present invention may be a polymer material having organometallic end groups, or may be an end-stabilized polymer material that has undergone an optional non-polymerizable reaction step. Moreover, the polymer material containing the said polymer manufactured by combining the polymerization process of this invention and other polymerization processes may be sufficient.
• the propylene polymer material of the present invention is: A propylene polymer material that satisfies the following requirements (a) and (b).
• (a) The ratio of zinc atoms/aluminum atoms in the propylene polymer material is 1.1 to 15 (mol-Zn/mol-Al).
• (b) Mw/Mn is 2.5 to 4.5.
• the zinc atoms and aluminum atoms in the propylene polymer material each exist in the form of being incorporated into the propylene polymer and in the form of a composition of the propylene polymer and catalyst residue.
• the ratio of zinc atoms/aluminum atoms in the propylene polymer material (a) is preferably 1.2 to 10 (mol-Zn/mol-Al).
• the above (b) Mw/Mn is preferably 2.6 to 4.4.
• the propylene polymer material of the present invention preferably contains zinc atoms in the (c) propylene polymer at a concentration of 20 to 1000 (mmol-Zn/kg-PP), preferably 20 to 500 (mmol-Zn/kg-PP). It is more preferable to include it at a concentration of PP).
• the propylene polymer material of the present invention preferably contains aluminum atoms in the propylene polymer material (d) at a concentration of 1 to 30 (mmol-Al/kg-PP), preferably 2 to 30 (mmol-Al/kg-PP). -PP).
• Active proton compounds that can be used in any non-polymerizable reaction step include water (including, for example, atmospheric moisture, hydrous nitrogen gas, boiled water, etc.), alcohols (ethanol, boiled ethanol, methanol, etc.). , boiled methanol, isopropyl alcohol, boiled isopropyl alcohol, etc.), hydrocarbons with active protons (such as toluene), carboxylic acids (such as acetic acid), inorganic acids (such as concentrated hydrochloric acid, carbonic acid, etc.), etc. be able to.
• Preferred active proton compounds are water, methyl alcohol, ethyl alcohol, isopropyl alcohol, and n-butyl alcohol, More preferred are water, methyl alcohol, and ethyl alcohol, More preferred is water.
• Reactive gas compounds that can be used in any non-polymerizable reaction step include oxygen gas, carbon dioxide gas, carbon monoxide gas, ozone gas, fluorine gas, chlorine gas, bromine gas, iodine gas, ethylene oxide gas, propylene oxide.
• Examples include methyl acrylate gas, methyl methacrylate gas, acrylonitrile gas, hydrogen cyanide gas, formaldehyde gas, methyl isocyanate gas, carbon disulfide gas, and mixtures thereof.
• the reactive gas compound is oxygen gas, carbon dioxide gas, or a mixture of oxygen gas and carbon dioxide gas, More preferred is oxygen gas.
• the reactive gas compound may be a mixed gas containing an inert gas such as nitrogen gas or argon gas.
• the mixed gas is preferably nitrogen gas or argon gas, more preferably nitrogen gas.
• the volume fraction of the reactive gas compound in the mixed gas is preferably 0.001 to 99.9%. More preferably 0.001 to 80.0%, still more preferably 0.001 to 30%, particularly preferably 0.01 to 15 vol%, and most preferably 1 to 3 vol%. %.
• the reactive gas compound is oxygen gas
• a mixed gas containing oxygen gas at a lower concentration than air is preferred
• the reactive gas compound is carbon dioxide gas
• a mixed gas containing carbon dioxide gas at a higher concentration than in the atmosphere is preferred.
• the polymeric material having organometallic end groups is treated with a reactive gas compound in any non-polymerizable reaction step, it is preferably carried out under conditions of a total pressure of 3 MPa or less.
• a total pressure 3 MPa or less.
• an expensive reaction vessel that can handle high pressure is required, which is unfavorable from an economic point of view.
• the time for treatment with the reactive gas compound is preferably 1 to 120 minutes. More preferably, the time is 1 to 90 minutes. More preferably, the time is 1 to 60 minutes.
• the polymeric material with organometallic end groups is treated with a reactive gas compound in any non-polymerizable reaction step, it is preferred that it is further treated with an active proton compound.
• the time for treatment with the active proton compound is preferably 1 to 120 minutes. More preferably, the time is 1 to 90 minutes. More preferably, the time is 1 to 60 minutes.
• the treatment with the reactive gas compound and the treatment with the active proton compound may be carried out simultaneously. That is, polymeric materials having organometallic end groups may be treated with a mixture of reactive gas compounds and active proton compounds. In this case, the number of processes can be reduced, which is preferable in terms of efficiency and economy.
• the terminally stabilized polymeric material that has undergone the optional non-polymerizable reaction step is further treated in a step to remove volatile compounds.
• processes for removing volatile compounds include a method of reducing pressure while heating, a method of circulating nitrogen gas while heating, and a method of continuously extracting and removing with heated water or heated alcohol, followed by reducing pressure or nitrogen gas. There are several methods of distribution.
• Volatile compounds include (a) diluting solvents such as propylene, hydrogen gas, hexane, and heptane; (b) ethanol and low-molecular (oligomer) alcohols produced from unreacted diethylzinc compounds or triethylaluminum and oxygen gas; (2-methyl-1-butanol, 2-methyl-1-pentanol, etc.), (c) active proton compounds such as water and ethanol added in the non-polymerizable reaction step. If (b) remains in the propylene polymer material, it may impede the performance of the propylene polymer material or may give off an odor to the propylene polymer material.
• the time for the step of removing volatile compounds is 1 to 120 minutes. More preferably, the time is 1 to 90 minutes. More preferably, the time is 1 to 60 minutes.
• (A) is 0.010 or more, and (B)/(A) is 0.40 or more.
• (A) The ratio of the number of organometallic end groups to the number of starting ends of the propylene polymer material
• (B) The ratio of the number of organometallic end groups to the number of starting ends of the specific high molecular weight fraction of the propylene polymer material (A) is: It is preferably 0.020 to 0.90, more preferably 0.030 to 0.80, even more preferably 0.040 to 0.50, and most preferably 0.050 to 0.25.
• (B)/(A) is preferably 0.50 to 1.0, more preferably 0.60 to 1.0, and even more preferably 0.70 to 1.0.
• the propylene polymer material of the present invention preferably has a color difference ⁇ E * ab between the propylene polymer material and a standard white plate of 0 to 10 in (f) L * a * b * color space, and the color difference ⁇ E*ab is more preferably from 0 to 6. More preferably 1 to 6, most preferably 1 to 3.
• the propylene polymer material of the present invention preferably has a chroma C * value of 0 to 4.0 in (g) L * a * b * color space, and a chroma C* value of 0 to 3. More preferably, it is .0. More preferably it is 0 to 2.0, most preferably 0.5 to 1.5.
• the propylene polymer material of the present invention preferably has a value of coordinate b * of -1.0 to 3.0 in (h) L * a * b * color space, and a value of -1 More preferably, it is between .0 and 2.0. More preferably it is 0 to 2.0, most preferably 0.5 to 1.5.
• the smaller the absolute value the closer to white the color is, which is preferable. That is, the smaller the absolute values of the color difference ⁇ E*ab and the saturation C * , the more difficult it is to visually distinguish the color from the standard white plate, which is preferable.
• the larger the absolute value the easier it is to distinguish, which is not preferable.
• the propylene polymer material after stabilization in any non-polymerizable reaction step including treatment with a reactive gas compound preferably contains a polymer chain having a hydroxyl group at the end.
• Such propylene polymer materials include propylene homopolymers and propylene/ethylene copolymers (random copolymers).
• the ratio (A) of the number of terminal hydroxyl groups to the number of starting terminals of the propylene polymer material in the propylene polymer material having hydroxyl groups is preferably 0.01 to 0.90. More preferably 0.02 to 0.70, still more preferably 0.03 to 0.50, particularly preferably 0.04 to 0.30, and most preferably 0.05 to 0.25. be.
• the melting point (Tm) of the propylene polymer material of the present invention is preferably 150 to 170°C, more preferably 158 to 170°C, even more preferably 160 to 168°C, and even more preferably 161 to 168°C. Most preferably. It is preferable that a sub-peak with lower intensity than the main peak exists on the higher temperature side than the main peak of the melting point.
• the secondary peak is preferably 155 to 175°C, more preferably 163 to 170°C, even more preferably 164 to 170°C, and most preferably 165 to 170°C.
• the heat of fusion ( ⁇ H) of the propylene polymer material of the present invention is preferably 80 to 150, more preferably 100 to 135.
• the number average molecular weight (Mn) of the propylene polymer material of the present invention is preferably 10,000 to 500,000, more preferably 20,000 to 200,000, and more preferably 20,000 to 100,000. It is more preferably 20,000 to 80,000, most preferably 20,000 to 40,000.
• the propylene polymer material of the present invention can be mixed with known additives in a powder state or a hot molten state.
• additives include neutralizing agents, antioxidants, ultraviolet absorbers, light stabilizers, anti-blocking agents, processing aids, organic peroxides, colorants (inorganic pigments, organic pigments, pigment dispersants, etc.) ), foaming agents, foaming nucleating agents, plasticizers, flame retardants, crosslinking agents, crosslinking aids, brightening agents, antibacterial agents, light diffusing agents, inorganic fillers, anti-scratch agents, and the like. Only one type of these additives may be mixed, or two or more types may be mixed.
• propylene polymer material of the present invention can be mixed with a different propylene polymer material of the present invention or other known polymer materials in a powder state or a hot molten state.
• the method for producing the propylene polymer material of the present invention is not particularly limited, but it can be produced by the production method mentioned in the above [Method for producing propylene polymer material].
• Elemental analysis in propylene polymer material The content of zinc atoms and aluminum atoms in propylene polymer material can be determined by subjecting the propylene polymer material to acid decomposition, followed by alkali melting, as a measurement sample liquid, and inductively bonding Measured by plasma emission spectrometry (ICP-AES method).
• the mobile phase was orthodichlorobenzene (dibutylhydroxytoluene was added as an antioxidant at 0.1 w/v), the flow rate was 1 mL/min, the column oven temperature was 140 °C, the autosampler temperature was 140 °C, and the system oven temperature was 40 °C. It was set at °C.
• a differential refractive index detector (RID) was used as a detector, the RID cell temperature was 140° C., and the sample solution injection amount was 300 ⁇ L. The obtained measured value was multiplied by a Q factor value of 26.4 to obtain the molecular weight in terms of polypropylene.
• L * 1 , a * 1 and b * 1 indicate the coordinates in the L * a * b * color space of the propylene polymer material.
• L * 2 , a * 2 and b * 2 indicate the coordinates of the standard white board in the L * a * b * color space.
• Intrinsic viscosity [ ⁇ ]T, unit: dL/g)
• the intrinsic viscosity of the propylene polymer material was determined using an Ubbelohde viscometer under three conditions: solvent: tetralin, temperature: 135°C, concentration: 0.1 g/dL, 0.2 g/dL, and 0.5 g/dL.
• the reduced viscosity of the propylene polymer material was measured.
• the reduced viscosity of the propylene polymer material was plotted against the concentration according to the calculation method described in "Polymer Solution, Polymer Experimental Science 11" (published by Kyoritsu Publishing Company, 1982), page 491, and the concentration was set to zero.
• the intrinsic viscosity of the propylene polymer material was determined by extrapolation.
• Intrinsic viscosity of propylene polymer component (A) ([ ⁇ ]A, unit: dL/g)) and limiting viscosity of propylene polymer component (B) ([ ⁇ ]B (unit: dL/g))
• the propylene polymer material is produced by a multi-stage polymerization method, with the propylene polymer component (A) produced in the first stage polymerization tank and the propylene polymer component (B) produced in the second stage polymerization tank.
• [ ⁇ ]A was determined by extracting the propylene polymer component (A) from the polymerization tank and measuring it by the method described in (4) above.
• [ ⁇ ]B was calculated using the following formula using [ ⁇ ]T, [ ⁇ ]A, and the polymerization ratio ( ⁇ ) of the propylene polymer component (B).
• melt flow rate (MFR (unit: g/10 minutes)
• the melt flow rate of the propylene polymer material was measured according to JIS K7210 at a temperature of 230° C. and a load of 2.16 kgf.
• CXS cold xylene soluble portion
• Liquid chromatography method Liquid chromatography was performed using an HPLC device (manufactured by Shimadzu Corporation) under the following conditions. SHODEX GPC KF-801 (upper exclusion limit molecular weight 1500) was used as the column, and tetrahydrofuran was used as the eluent. The column oven temperature was 40° C., the sample injection amount was 130 ⁇ L, the flow rate was 1 ml/min, and a differential refractometer (RI) was used as the detector. The measurements were performed using the following equipment.
• Liquid pump LC-20AD (manufactured by Shimadzu Corporation)
• Degasser DGU-20A3 (manufactured by Shimadzu Corporation)
• Auto sampler SIL-20A HT (manufactured by Shimadzu Corporation)
• Column oven CTO-20A (manufactured by Shimadzu Corporation)
• Differential refractive index detector RID-10A (manufactured by Shimadzu Corporation)
• System controller CBM-20A (manufactured by Shimadzu Corporation)
• Static bulk density (10) Static bulk density (SBD, unit: g/mL) The static bulk density of the propylene polymer material was measured according to the method specified in JIS K 6722.
• Ratio of the number of organometallic end groups to the number of starting ends of the propylene polymer material is the ratio of the number of organometallic end groups to the number of starting ends of the propylene polymer material.
• the starting end integral value and the organometallic end (hydroxyl group end) integral value of the propylene polymer material were determined.
• Starting terminal integral value a4 + (a2 + a5)/2
• Organometallic end (hydroxyl end) integral value (a1+a3)/2
• the ratio of the number of organometallic terminal groups to the number of starting terminals of the propylene polymer material was determined from the ratio of the integral value of organometallic terminals (hydroxyl group terminals) to the integral value of the starting terminals.
• a solid catalyst component for olefin polymerization was obtained according to the method described in Example 1 of JP-A-2009-173870.
• the prepolymerized slurry is transferred to a SUS autoclave with an internal volume of 200L and equipped with a stirrer, and 132L of sufficiently purified liquid butane is added to form a slurry of prepolymerized catalyst components, which is maintained at a temperature of 10°C or less and stored. did.
• Propylene polymerization (liquid phase polymerization reaction) Propylene homopolymerization was performed using a loop reactor with a total internal capacity of 30 L. A slurry of propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, diethylzinc, and the prepolymerized catalyst components prepared above is continuously supplied to the reactor, and polymerization is carried out in a full liquid state without the presence of a gas phase. did.
• reaction conditions were: polymerization temperature: 70°C, pressure: 4.4 MPaG, propylene supply rate: 78 kg/hour, hydrogen supply rate: 49.4 NL/hour, triethylaluminum supply rate: 36.8 mmol/hour (hexane solution), cyclohexylethyldimethoxysilane supply amount: 5.5 mmol/hour (hexane solution), diethylzinc: 200 mmol/hour (hexane solution), supply amount of prepolymerized catalyst component slurry (in terms of solid catalyst component) : 0.57 g/hour. Note that a separate input line was used to supply diethylzinc to the reactor.
• the amount of propylene polymer material 1 continuously discharged from the reactor was 3.6 kg/hour and was continuously transferred to the work-up step. While continuously receiving the obtained propylene polymer material 1, nitrogen at 60° C. was passed for 2 hours at a flow rate of 20 Nm 3 /h, and then nitrogen at 60° C. was passed for 1 hour at a flow rate of 20 Nm 3 /h to dry it. After that, it was brought into contact with undried air containing oxygen and water. The results are shown in Tables 1-11.
• Propylene polymerization (liquid phase polymerization reaction) Propylene homopolymerization was performed using a loop reactor with a total internal capacity of 30 L. A slurry of propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, diethylzinc, and the prepolymerized catalyst components prepared above is continuously supplied to the reactor, and polymerization is carried out in a full liquid state without the presence of a gas phase. did.
• reaction conditions were: polymerization temperature: 70°C, pressure: 4.4 MPaG, propylene supply rate: 78 kg/hour, hydrogen supply rate: 100.9 NL/hour, triethylaluminum supply rate: 36.8 mmol/hour (hexane solution), cyclohexylethyldimethoxysilane supply amount: 5.5 mmol/hour (hexane solution), diethylzinc: 100 mmol/hour (hexane solution), supply amount of prepolymerized catalyst component slurry (in terms of solid catalyst component) : 0.58 g/hour. Note that a separate input line was used to supply diethylzinc to the reactor.
• the amount of propylene polymer material 2 continuously discharged from the reactor was 4.2 kg/hour and was continuously transferred to the work-up stage. While continuously receiving the obtained propylene polymer material 2, nitrogen at 60° C. was passed for 2 hours at a flow rate of 20 Nm 3 /h, and then nitrogen at 60° C. was passed for 1 hour at a flow rate of 20 Nm 3 /h to dry it. After that, it was brought into contact with undried air containing oxygen and water. The results are shown in Tables 1-11.
• Propylene polymerization (liquid phase polymerization reaction) Propylene homopolymerization was performed using a loop reactor with a total internal capacity of 30 L. A slurry of propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, diethylzinc, and the prepolymerized catalyst components prepared above is continuously supplied to the reactor, and polymerization is carried out in a full liquid state without the presence of a gas phase. did.
• reaction conditions were: polymerization temperature: 70°C, pressure: 4.4 MPaG, propylene supply rate: 39 kg/hour, hydrogen supply rate: 24.2 NL/hour, triethylaluminum supply rate: 36.8 mmol/hour (hexane solution), cyclohexylethyldimethoxysilane supply amount: 5.5 mmol/hour (hexane solution), diethylzinc: 200 mmol/hour (hexane solution), supply amount of prepolymerized catalyst component slurry (in terms of solid catalyst component) :0.60g/hour. Note that a separate input line was used to supply diethylzinc to the reactor.
• the amount of propylene polymer material 3 continuously discharged from the reactor was 7.4 kg/hour and was continuously transferred to the work-up stage. While continuously receiving the obtained propylene polymer material 3, nitrogen at 60° C. was passed for 2 hours at a flow rate of 20 Nm 3 /h, and then nitrogen at 60° C. was passed for 1 hour at a flow rate of 20 Nm 3 /h to dry it. After that, it was brought into contact with undried air containing oxygen and water. The results are shown in Tables 1-11.
• Propylene polymerization (liquid phase polymerization reaction) Propylene homopolymerization was performed using a loop reactor with a total internal capacity of 30 L. A slurry of propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, diethylzinc, and the prepolymerized catalyst components prepared above is continuously supplied to the reactor, and polymerization is carried out in a full liquid state without the presence of a gas phase. did.
• reaction conditions were: polymerization temperature: 70°C, pressure: 4.4 MPaG, propylene supply rate: 156 kg/hour, hydrogen supply rate: 101.4 NL/hour, triethylaluminum supply rate: 36.8 mmol/hour (hexane solution), cyclohexylethyldimethoxysilane supply amount: 5.5 mmol/hour (hexane solution), diethylzinc: 200 mmol/hour (hexane solution), supply amount of prepolymerized catalyst component slurry (in terms of solid catalyst component) : 0.61 g/hour. Note that a separate input line was used to supply diethylzinc to the reactor.
• the amount of propylene polymer material 4 continuously discharged from the reactor was 1.9 kg/hour and was continuously transferred to the work-up step. While continuously receiving the obtained propylene polymer material 4, nitrogen at 60° C. was passed for 2 hours at a flow rate of 20 Nm 3 /h, and then nitrogen at 60° C. was passed for 1 hour at a flow rate of 20 Nm 3 /h to dry it. After that, it was brought into contact with undried air containing oxygen and water. The results are shown in Tables 1-11.
• Propylene polymerization (liquid phase polymerization reaction) Propylene homopolymerization was performed using a loop reactor with a total internal capacity of 30 L. A slurry of propylene, triethylaluminum, cyclohexylethyldimethoxysilane, diethylzinc, and the prepolymerized catalyst components prepared above was continuously supplied to the reactor, and polymerization was carried out in a full liquid state in the absence of a gas phase.
• reaction conditions were: polymerization temperature: 70°C, pressure: 4.4 MPaG, propylene supply rate: 78 kg/hour, triethylaluminum supply rate: 36.8 mmol/hour (hexane solution), cyclohexylethyldimethoxysilane supply rate: 5.5 mmol/hour (hexane solution), diethyl zinc: 200 mmol/hour (hexane solution), and supply amount of prepolymerized catalyst component slurry (in terms of solid catalyst component): 0.58 g/hour. Note that a separate input line was used to supply diethylzinc to the reactor.
• the amount of propylene polymer material 5 continuously discharged from the reactor was 1.4 kg/hour and was continuously transferred to the work-up step. While continuously receiving the obtained propylene polymer material 5, nitrogen at 60° C. was passed for 2 hours at a flow rate of 20 Nm 3 /h, and then nitrogen at 60° C. was passed for 1 hour at a flow rate of 20 Nm 3 /h to dry it. After that, it was brought into contact with undried air containing oxygen and water. The results are shown in Tables 1-12.
• the prepolymerized slurry is transferred to a SUS autoclave with an internal volume of 200L and equipped with a stirrer, and 132L of sufficiently purified liquid butane is added to form a slurry of prepolymerized catalyst components, which is maintained at a temperature of 10°C or less and stored. did.
• Propylene polymerization (liquid phase polymerization reaction) Propylene homopolymerization was performed using a loop reactor with a total internal capacity of 30 L. A slurry of propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, diethylzinc, and the prepolymerized catalyst components prepared above is continuously supplied to the reactor, and polymerization is carried out in a full liquid state without the presence of a gas phase. did.
• reaction conditions were: polymerization temperature: 70°C, pressure: 4.4 MPaG, propylene supply rate: 78 kg/hour, hydrogen supply rate: 155.0 NL/hour, triethylaluminum supply rate: 36.8 mmol/hour (hexane solution), cyclohexylethyldimethoxysilane supply amount: 5.5 mmol/hour (hexane solution), diethylzinc: 52 mmol/hour (hexane solution), supply amount of prepolymerized catalyst component slurry (in terms of solid catalyst component) : 0.58 g/hour. Note that a separate input line was used to supply diethylzinc to the reactor.
• the amount of propylene polymer material 6 continuously discharged from the reactor was 1.4 kg/hour and was continuously transferred to the work-up step. While continuously receiving the obtained propylene polymer material 6, nitrogen at 60° C. was passed for 2 hours at a flow rate of 20 Nm 3 /h, and then nitrogen at 60° C. was passed for 1 hour at a flow rate of 20 Nm 3 /h to dry it. After that, it was brought into contact with undried air containing oxygen and water. The results are shown in Tables 1-12.
• the reaction conditions were: polymerization temperature: 70°C, pressure: 4.4 MPaG, propylene supply rate: 78 kg/hour, hydrogen supply rate: 50.8 NL/hour, triethylaluminum supply rate: 36.8 mmol/hour (hexane solution), cyclohexylethyldimethoxysilane supply amount: 5.5 mmol/hour (hexane solution), supply amount of prepolymerized catalyst component slurry (in terms of solid catalyst component): 0.57 g/hour.
• the amount of propylene polymer component (A) continuously discharged from the reactor was 3.5 kg/hour.
• the obtained slurry containing the propylene polymer component (A) was continuously transferred to the second step reactor without being deactivated.
• the slurry containing the discharged propylene polymer component (A) was continuously polymerized. Note that a separate input line was used to supply diethylzinc to the reactor.
• the amount of propylene polymer material 7 continuously discharged from the reactor was 10.6 kg/h and was continuously transferred to the work-up stage. While continuously receiving the obtained propylene polymer material 7, nitrogen at 60° C. was passed for 2 hours at a flow rate of 20 Nm 3 /h, and then nitrogen at 60° C. was passed for 1 hour at a flow rate of 20 Nm 3 /h to dry it. After that, the mixture was brought into contact with undried air containing oxygen and water to obtain propylene polymer material 7-A.
• Propylene polymerization (liquid phase polymerization reaction) Propylene homopolymerization was performed using a loop reactor with a total internal capacity of 30 L. A slurry of propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, and the prepolymerized catalyst component prepared above was continuously supplied to the reactor, and polymerization was carried out in a full liquid state without the presence of a gas phase.
• the reaction conditions were: polymerization temperature: 70°C, pressure: 4.4 MPaG, propylene supply rate: 78 kg/hour, hydrogen supply rate: 209.9 NL/hour, triethylaluminum supply rate: 36.8 mmol/hour (hexane solution), cyclohexylethyldimethoxysilane supply amount: 5.5 mmol/hour (hexane solution), supply amount of prepolymerized catalyst component slurry (in terms of solid catalyst component): 1.27 g/hour.
• the amount of propylene polymer material C1 continuously discharged from the reactor was 8.8 kg/hour and was continuously transferred to the work-up stage. While continuously receiving the obtained propylene polymer material C1, nitrogen at 60° C.
• Example 7B From the results of Example 7B in Table 12, by treating the polymer material having organometallic end groups with an active proton compound (ethanol), a propylene polymer with saturated terminals in which the organometallic end groups were protonated was obtained. It can be seen that the material is being generated.
• an active proton compound ethanol
• Example 7A in Table 12 From the results of Example 7A in Table 12, it can be seen that the production method described in the present application produces a propylene polymer material within the scope of claim 8, From the results of Comparative Example 5 in Table 12, it can be seen that the propylene polymer material within the scope of claim 8 is not produced by the known production method.
• the propylene polymer material of the present invention can be molded into parts for products such as electrical products and automobiles by molding methods such as injection molding, injection compression molding, gas-assisted molding, and extrusion molding.
• various interior and exterior parts of automobiles such as instrument panels, glove boxes, trims, housings, pillars, bumpers, fenders, back doors, etc., various parts of home appliances, various housing equipment parts, etc. It is suitably used for applications such as industrial parts and various building material parts, and has high applicability in various industrial fields such as the transportation machinery industry, the electrical and electronic industry, and the building construction industry. , instrument panels, and automobile parts such as bumpers.

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