WO2023190469A1 - Procédé de production de polyoléfine modifiée - Google Patents

Procédé de production de polyoléfine modifiée Download PDF

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WO2023190469A1
WO2023190469A1 PCT/JP2023/012415 JP2023012415W WO2023190469A1 WO 2023190469 A1 WO2023190469 A1 WO 2023190469A1 JP 2023012415 W JP2023012415 W JP 2023012415W WO 2023190469 A1 WO2023190469 A1 WO 2023190469A1
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modified polyolefin
gas
compound
producing
group
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PCT/JP2023/012415
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Japanese (ja)
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和夫 高沖
伸一 熊本
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住友化学株式会社
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    • 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
    • C08F8/00—Chemical modification by after-treatment

Definitions

  • This invention relates to a method for producing modified polyolefins (for example, polyolefins whose terminals are -OZnOEt groups and polyolefins whose terminals are hydroxyl groups) using a Ziegler-Natta catalyst and an organozinc compound.
  • modified polyolefins for example, polyolefins whose terminals are -OZnOEt groups and polyolefins whose terminals are hydroxyl groups
  • Non-Patent Document 1 describes the preparation of polypropylene having a hydroxyl group at the end.
  • Non-Patent Document 1 polypropylene having a hydroxyl group at the terminal is prepared in a mixed gas atmosphere of oxygen gas (0.5% by volume) and nitrogen gas (99.5% by volume) (iPP-OH (2) ), the reaction is carried out under high pressure (45-46 bar), and the reaction is carried out under conditions in which there are substantially many reactive gas compounds, and the reaction is not described under low pressure (3 MPa or less).
  • polypropylene with a hydroxyl group at the end is prepared by treating a propylene polymer with a metal-containing end group with acidic methanol (iPP-OH (3)), but the atmosphere is not described. It has not been.
  • the problems to be solved by the present invention are economical (i.e., low in reactive gas compounds (oxygen gas)), safety, and quality of the resulting modified polyolefin (function as a compatibilizer,
  • the object of the present invention is to provide a method for producing a modified polyolefin, which is excellent in properties such as reactivity of terminal polar groups, low odor, etc.).
  • [3] The modified polyolefin according to [1] or [2], wherein the value of A/B is 1 to 100,000, where A is the molar amount of the reactive gas compound and B is the molar amount of the organic metal. manufacturing method.
  • [4] The method for producing a modified olefin according to any one of [1] to [3], wherein the time of the step (1) is 1 to 120 minutes.
  • [5] The method for producing a modified polyolefin according to any one of [1] to [4], further comprising a step (2) of treating the modified polyolefin obtained in the step (1) with an active proton compound.
  • [6] The method for producing a modified polyolefin according to [5], wherein the time of the step (2) is 1 to 120 minutes.
  • the olefin polymer having an organometallic end group is obtained by polymerizing an olefin in the presence of a solid catalyst component for olefin polymerization, an organoaluminum compound, and an organozinc compound, [1] to [11] ]
  • the modified polyolefin described in [13] which satisfies the following conditions. (Conditions)
  • the value of E/F (Mz ratio) when using the same raw materials is 1.0 to 4.0.
  • Mz F Mz of modified polyolefin synthesized using O2 with a volume fraction of 100 vol% [15]
  • G modified polyolefin synthesized using O2 at a volume fraction of 0.01 to 15 vol%.
  • Mw H Mw of modified polyolefin synthesized using O2 with a volume fraction of 100 vol% [16]
  • the manufacturing method of the present invention is as follows: A step (1) of treating an olefin polymer having an organometallic end group with a mixed gas containing a reactive gas compound and an inert gas, wherein the volume fraction of the reactive gas compound in the mixed gas is 0. A method for producing a modified polyolefin having a content of .01 to 15 vol%.
  • Step (1)> ⁇ Olefin polymer having organometallic terminal group>
  • organic metals can be exemplified, such as the residues of organic zinc compounds, the residues of organic aluminum compounds, and the residues of organic magnesium compounds, which are explained in the section " ⁇ Organozinc compounds>" below. can do.
  • the metal in the olefin polymer having organometallic end groups is a zinc atom.
  • organometallic terminal groups can be exemplified, such as -ZnEt group, -ZnMe group, -ZniPr group, -ZnnBu group, and -ZniBu group shown in the following chemical formula. be able to.
  • the olefin polymer having an organometallic end group used in the production method of the present invention and the modified polyolefin produced include, for example, organometallic end group polypropylene shown by the chemical formula below, and , modified polypropylene can be exemplified.
  • the olefin polymer having an organometallic terminal group is preferably obtained by polymerizing an olefin in the presence of a solid catalyst component for olefin polymerization, an organoaluminum compound, and an organozinc compound.
  • the method for producing an olefin polymer having an organometallic terminal group is not particularly limited, but for example, an olefin polymer having an organometallic terminal group can be produced by the following method for producing a propylene polymer material. .
  • the solid catalyst component for olefin polymerization used preferably contains titanium atoms and magnesium atoms.
  • methods for preparing the solid catalyst component for olefin polymerization to be used include the following methods (1) to (5): (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 oxy group, a halogenated compound, and an internal electron donor and/or an
  • 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 include trialkylaluminums such as trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; diethylaluminum monochloride, diisobutylaluminum monochloride, Alkylaluminium halides such as ethylaluminum sesquichloride and ethylaluminum dichloride; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; aluminum alkoxides such as diethylaluminum ethoxide and diethylaluminium phenoxide; methylalumoxane, ethylaluminum Alumoxanes such as xane, iso
  • 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;
  • 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.
  • 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.
  • Organozinc compounds used in the process for producing olefin polymers having organometallic end groups include dimethylzinc, diethylzinc, di-n-propylzinc, di-n-butylzinc, diisobutylzinc, and di-n- - dialkylzincs such as hexylzinc; diarylzincs such as diphenylzinc and dinaphthylzinc; bis(cyclopentadienyl)zinc; and dialkenylzincs such as diallyzinc.
  • 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 in the method for producing olefin polymers having organometallic terminal groups, such as ethylene, 1-butene, 1-pentene, etc. , 1-hexene, 1-heptene, 1-octene, and 1-decene; such as 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl-1-pentene.
  • organometallic terminal groups such as ethylene, 1-butene, 1-pentene, etc. , 1-hexene, 1-heptene, 1-octene, and 1-decene; such as 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl-1-pentene.
  • Examples include branched olefins; alicyclic olefins such as vinylcyclohexane; and combinations of two or more of these.
  • homopolymerization of propylene, ethylene, 1-butene, 1-hexene, propylene/ethylene, propylene/1-butene, propylene/ethylene/1-butene, ethylene/1-butene, ethylene/4-methyl-1- Examples include copolymers of pentene, ethylene/1-hexene, ethylene/1-butene/1-hexene, and the like.
  • 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 proportion 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 olefin polymer having organometallic end groups is preferably a homopolymer of propylene, or a propylene-ethylene copolymer, a propylene-1-butene copolymer, and a propylene-1-hexene copolymer. , 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 usually 0.01 to 10 wt%, preferably 0.1 to 8 wt%, based on 100 wt% of the copolymer.
  • ⁇ Continuous supply process> and ⁇ Continuous removal process> The internal homogeneity of the reactor used in the continuous supply process and continuous withdrawal process of the method for producing olefin polymers having organometallic end groups is maintained by stirring, etc. in the liquid phase, and gas flow, etc. in the gas phase.
  • This is a reactor.
  • 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 continuous supply step, it is preferable that the organoaluminum compound and the organozinc compound are continuously supplied to the reactor using separate lines.
  • the organozinc compound when the impurity (eg, AlHEt 2 ) contained in the organoaluminum compound (eg, AlEt 3 ) reacts with the organozinc compound, the organozinc compound is reduced to zinc. Since zinc is gray in color, it colors the propylene polymer material produced. Such coloring can be avoided if the organoaluminum compound and the organozinc compound are fed into the reactor through separate lines.
  • a propylene polymer material is obtained through a process (polymerization process) in which propylene continuously supplied in a continuous supply process is polymerized in a reactor, and then the propylene polymer material obtained in the reactor is transferred from the reactor. Take out continuously.
  • 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 0.1 to 1000 (mmol-Zn/kg-PP), and 1 to 800 (mmol-Zn/kg-PP). It is preferably 20 to 500 (mmol-Zn/kg-PP), and more preferably 20 to 500 (mmol-Zn/kg-PP).
  • the feed rate of the organozinc compound relative to the feed rate of the organoaluminum compound is preferably 0.1 to 15 (mol-Zn/mol-Al), and preferably 0.2 to 12 (mol-Zn /mol-Al), and even more preferably 1.1 to 10 (mol-Zn/mol-Al). It is preferable that 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 method for producing an olefin polymer having an organometallic end group is one or more.
  • the number of steps is two 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.
  • 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 organoaluminum compound used is usually 1 to 1 per mole of titanium atom in the solid catalyst component.
  • the amount is 1000 mol, preferably 5 to 600 mol.
  • 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.
  • the polymerization time is usually 0.2 to 10 hours. Preferably it is 0.5 to 6 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.
  • the phase polymerization method or a method combining two or more of these methods is carried out in a batch method, 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 adjust the molecular weight of the olefin polymer 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 obtained olefin polymer powder.
  • the organoaluminum compound in the main polymerization is not essential.
  • olefin a small amount of olefin (same or different from the olefin used in the main polymerization) in the presence of a solid catalyst component and an organoaluminum compound.
  • the solvent used for slurrying include inert hydrocarbon solvents such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Part or all of the solvent can be replaced with a liquid olefin.
  • 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 olefin polymer and olefin generally coexist under high pressure, but before contacting the reactive gas compound, they are
  • the olefin may be separated by a degassing operation, or may be replaced with an inert gas or the like.
  • ⁇ Mixed gas containing reactive gas compound and inert gas examples include oxygen gas, carbon dioxide gas, carbon monoxide gas, ozone gas, fluorine gas, chlorine gas, bromine gas, iodine gas, ethylene oxide gas, propylene oxide gas, methyl acrylate gas, methyl methacrylate gas, Examples include acrylonitrile gas, hydrogen cyanide gas, formaldehyde gas, methyl isocyanate gas, and carbon disulfide gas. It is preferable that the reactive gas compound is at least one gas selected from the group consisting of oxygen gas and carbon dioxide gas. Examples of the inert gas include nitrogen gas and argon gas. The volume fraction of the reactive gas compound in the mixed gas is 0.01 to 15 vol%.
  • the volume fraction is preferably 0.05 to 15 vol%, more preferably 1 to 10 vol%, even more preferably 1 to 5 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 preferable
  • the reactive gas compound is carbon dioxide gas
  • a mixed gas containing carbon dioxide gas at a higher concentration than air is preferable.
  • a mixed gas containing gas is preferred.
  • the reactive gas is oxygen gas
  • a concentration of 0.01 vol% or less is not preferable because the desired modification will be difficult to proceed.
  • the resin will be decomposed by radical species caused by oxygen gas generated as a reaction intermediate, resulting in an unintended decrease in molecular weight and narrowing of the molecular weight distribution. This makes it difficult to obtain the desired structure (resulting in a decrease in quality).
  • E/F Mz ratio
  • E Mz of modified polyolefin synthesized using O2 at a volume fraction of 0.01 to 15 vol%
  • F Mz of modified polyolefin synthesized using O2 with a volume fraction of 100 vol%
  • the value of E/F is preferably 1.0 to 4.0, more preferably 1.1 to 3.0, even more preferably 1.4 to 2.8, and even more preferably 1.7 ⁇ 2.5 is most preferred.
  • G Mz of modified polyolefin synthesized using O2 with a volume fraction of 0.01 to 15 vol%
  • H Mz of modified polyolefin synthesized using O2 with a volume fraction of 100 vol%
  • the value of G/H is preferably 1.0 to 3.0, more preferably 1.1 to 2.5, even more preferably 1.1 to 2.0, and 1.4 ⁇ 1.8 is most preferred.
  • the step of treating with a mixed gas in step (1) is performed under conditions of a total pressure of 3 MPa or less.
  • a total pressure of 3 MPa or less In order to carry out the reaction under high pressure conditions, an expensive reaction vessel that can handle high pressure is required, which is unfavorable from an economic point of view.
  • the value of A/B is preferably 1 to 100,000.
  • the value of A/B is more preferably from 1 to 10,000, even more preferably from 1 to 1,000, particularly preferably from 1 to 100, and most preferably from 1 to 50.
  • the time for step (1) 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 method for producing a modified polyolefin of the present invention further includes a step (2) of treating the modified polyolefin obtained in the step (1) with an active proton compound.
  • Active proton compounds include, for example, water (including, for example, atmospheric moisture, hydrous nitrogen gas, boiled water, etc.), alcohols (ethanol, boiled ethanol, methanol, boiled methanol, isopropyl alcohol, boiled Examples include hydrocarbons having active protons (such as toluene), carboxylic acids (such as acetic acid), and inorganic acids (such as concentrated hydrochloric acid and carbonic acid).
  • water, ethanol, methanol, etc. are preferred.
  • the time for step (2) 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 method for producing a modified polyolefin of the present invention further includes a step (3) of removing volatile compounds from the modified polyolefin obtained in the step (1) or (2).
  • step (3) include a method of reducing the pressure while heating the modified polyolefin; Examples include a method of flowing nitrogen gas while heating the modified polyolefin, and a method of continuously extracting and removing volatile compounds from the modified polyolefin with heated water or heated alcohol, and then reducing the pressure or flowing nitrogen gas.
  • Volatile compounds include (a) diluent solvents such as propylene, hydrogen gas, hexane, and heptane, (b) ethanol generated from unreacted diethylzinc compound or triethylaluminum and oxygen gas, and low molecular weight (oligomer) PPOH. Possible examples include 2-methyl-1-butanol and 2-methyl-1-pentanol. If (b) remains in the modified polyolefin, it may hinder the functional expression of the modified polyolefin, or the modified polyolefin may have an odor.
  • the time for step (3) 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 method for producing a modified polyolefin of the present invention may include the following step (4):
  • a method for producing a modified polyolefin comprising a step (4) of treating an olefin polymer having organometallic end groups with a mixture of a reactive gas compound and an active proton compound. That is, step (4) is a step of treating an olefin polymer having an organometallic end group using a reactive gas compound and an active proton compound in combination, and the reaction with the reactive gas compound and the active proton compound is prevented. This is an efficient and economical method in which the reaction is performed in one step by selecting reaction conditions.
  • Typical reaction conditions for treatment step (4) are: an olefin polymer having organometallic end groups is separated into a flask in which the internal gas has been replaced with nitrogen gas, and a mixed gas of oxygen gas/nitrogen gas (oxygen Gas: 5.25 vol%, nitrogen gas: 94.75 vol%, dew point: -50.8°C) was flowed from the bottom of the olefin polymer having organometallic end groups at a flow rate of 200 mL/min, and the mixture was heated at 66°C for 30 minutes. , conditions for reacting an olefin polymer having an organometallic end group with oxygen gas.
  • the mixture of reactive gas compound and active protons used in step (4) has, for example, a water content (dew point) in oxygen gas of -80°C to 40°C.
  • the gas composition (dew point) of the mixture is, for example, -80 to 0°C, more preferably -80 to -10°C, and still more preferably -80 to -20°C.
  • the following propylene polymer materials can be exemplified: 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 preferably contains zinc atoms in the (c) propylene polymer at a concentration of 20 to 1000 (mmol-Zn/kg-PP), and preferably 20 to 500 (mmol-Zn/kg-PP). ) is more preferably included.
  • the propylene polymer material (d) preferably contains aluminum atoms in a concentration of 1 to 30 (mmol-Al/kg-PP), and preferably 2 to 30 (mmol-Al/kg-PP). It is more preferable to include it at a concentration of PP).
  • the propylene polymer material may be a propylene polymer composition of a propylene polymer and a catalyst residue.
  • the propylene polymer material preferably has a color difference ⁇ E*ab between the propylene polymer material and a standard white plate of 0 to 10 in the (f) L * a * b * color space, and the color difference ⁇ E*ab is 0 to 10. More preferably, it is 0-6.
  • the propylene polymer material 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 3.0. More preferably, it is 0.
  • the propylene polymer material preferably has a value of coordinate b* of -1.0 to 3.0 in ( h)L * a * b * color space, and a value of -1.0 to 3.0 for coordinate b*. More preferably, it is 0 to 2.0.
  • the color difference ⁇ E * ab and the chroma C * between the propylene polymer material and the standard white plate 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 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 above propylene polymer material is not particularly limited, but it can be produced by the production method mentioned in the above ⁇ Olefin polymer having organometallic terminal group>.
  • the above-mentioned propylene polymer material is preferable.
  • the modified polyolefin of the present invention is preferably a modified polyolefin having a hydroxyl group at one end (stopped end) of a propylene polymer.
  • propylene-based polymers include propylene homopolymers and propylene/ethylene copolymers (random copolymers).
  • the modified polyolefin of the present invention is preferably a modified polyolefin having a hydroxyl group at one end (terminal end) of a propylene homopolymer chain.
  • the terminated terminal OH conversion ratio of the modified polyolefin having a hydroxyl group is preferably 1 to 90%. It is more preferably 2 to 70%, still more preferably 3 to 50%, particularly preferably 4 to 30%, and most preferably 5 to 20%.
  • the melting point (Tm) of the modified polyolefin 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. is most preferable. 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 167 to 170°C.
  • the heat of fusion ( ⁇ H) of the modified polyolefin of the present invention is preferably 80 to 150, more preferably 100 to 135.
  • the weight average molecular weight (Mw) of the modified polyolefin of the present invention is: It is preferably from 5,000 to 1,000,000, More preferably, it is 10,000 to 800,000, More preferably, it is 20,000 to 700,000, Particularly preferably from 50,000 to 600,000, Most preferably, it is between 150,000 and 500,000.
  • the Z average molecular weight (Mz) of the modified polyolefin of the present invention is It is preferably from 10,000 to 2,000,000, More preferably, it is 20,000 to 1,500,000, More preferably, it is 50,000 to 1,200,000, Particularly preferably from 100,000 to 1,000,000, Most preferably, it is between 350,000 and 800,000.
  • the Mw/Mn of the modified polyolefin of the present invention is preferably 2.5 to 6.5, more preferably 2.6 to 6.0, and even more preferably 2.7 to 5.5. It is preferably from 2.8 to 5.0.
  • Mz/Mn of the modified polyolefin of the invention is preferably 4.0 to 30.0, more preferably 5.0 to 20.0, even more preferably 5.5 to 18.0. , 6.0 to 16.0 is most preferred.
  • the hydroxyl group content in the modified propylene polymer was measured by the following method.
  • Nuclear magnetic resonance in the 1 H nucleus of the modified propylene polymer was measured using 1 H-NMR, and when [integrated value of all peaks present at -0.5 to 5.5 ppm] was set to 100,000, [ The relative value of the integrated value of the peak existing at 3.2 to 3.5 ppm was calculated. At 3.2 to 3.5 ppm, an H signal of a methylene group (CH 2 OH) to which a hydroxyl group is bonded appears.
  • JNM-AL400 manufactured by JEOL was used for 1 H-NMR measurement. Measurements were carried out at 135°C using orthodichlorobenzene- d4 as a solvent.
  • ⁇ Ethylene content of propylene/ethylene random copolymer> The ethylene content (C2') of the propylene/ethylene random copolymer portion was determined from the 13C-NMR spectrum measured under the following conditions, based on the report by Kakugo et al. (Macromolecules 1982, 15, 1150-1152). A sample was prepared by uniformly dissolving approximately 250 mg of propylene/ethylene random copolymer in 2.5 mL of solvent in a 10 mm ⁇ test tube, and the 13C-NMR spectrum of the sample was measured under the following conditions.
  • the dew point of the mixed gas was measured using a portable dew point meter SADP ⁇ manufactured by SHAW.
  • the mixed gas was passed through the dew point meter, and continued to flow for 10 to 30 minutes until the value displayed on the device stabilized. After the value stabilized, the value displayed on the device was taken as the dew point of the mixed gas.
  • 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.
  • Mn, Mw, and Mz were calculated according to JIS K7252-1.
  • DSC differential scanning calorimeter
  • the temperature at the top of the melting peak in the melting curve was taken as the melting point of the propylene polymer material.
  • the peak with the highest intensity was defined as the main peak, and the peak with the next highest intensity was defined as the sub-peak.
  • the residue in the catalyst charger was poured into the autoclave using heptane (20 mL x 2). Thereafter, 780 g of propylene was added into the autoclave, and then 1.9 mL of diethylzinc (2.05 mol/L, hexane solution) was added. Thereafter, the autoclave was heated and propylene was polymerized at 80° C. for another 60 minutes. Thereafter, remaining flammable gases such as propylene and heptane were removed by purging propylene and reducing the pressure inside the autoclave at 64°C.
  • the combustible gas has been removed by closing the pressure reducing valve to create a closed system after the degree of vacuum in the autoclave reaches -0.100 MPa, and maintaining the degree of vacuum at -0.100 MPa for one minute. I checked it out.
  • a part (81.1 g) of the powdered propylene polymer having an organometallic end group (hereinafter also referred to as "PPZn powder") in the autoclave was Argon gas was fed under pressure to a flask in which the gas inside was replaced with nitrogen gas, and the flask was used in Examples and Comparative Examples described later.
  • PPZn powder powdered propylene polymer having an organometallic end group
  • Example 1 Production of modified propylene polymer 1> 9.7 g of a portion (81.1 g) of the PPZn powder obtained in Synthesis Example 2 was taken into a flask in which the gas inside was replaced with nitrogen gas, and a mixed gas of oxygen gas/nitrogen gas (oxygen Gas: 5.25 vol%, nitrogen gas: 94.75 vol%, dew point: -50.8°C) was passed from the bottom of the PPZn powder at a flow rate of 200 mL/min, and the PPZn powder and oxygen gas were heated at 66°C for 30 minutes. Made it react.
  • oxygen Gas 5.25 vol%
  • nitrogen gas 94.75 vol%
  • the flask was opened and the obtained reaction product was taken out. When taking it out, it was observed that the reactant adhered to the flask wall due to static electricity.
  • the hydrolysis reaction was allowed to proceed by bringing the extracted reactant into contact with moisture in the atmosphere.
  • the obtained reaction mixture was dried under reduced pressure at 80° C. to remove volatile compounds, and modified propylene polymer 1 was obtained.
  • Example 1 The results of Example 1 are shown in Tables 1, 2, 3 and 4.
  • Example 2 Production of modified propylene polymer 2> 9.6 g of a portion (81.1 g) of the PPZn powder obtained in Synthesis Example 2 was taken into a flask in which the gas inside was replaced with nitrogen gas, and a mixed gas of oxygen gas/nitrogen gas (oxygen Gas: 5.25 vol%, nitrogen gas: 94.75 vol%, dew point: -50.8°C) was passed from the bottom of the PPZn powder at a flow rate of 200 mL/min, and the PPZn powder and oxygen gas were heated at 101°C for 30 minutes. Made it react.
  • oxygen Gas 5.25 vol%
  • nitrogen gas 94.75 vol%
  • the flask was opened and the obtained reaction product was taken out. When taking it out, it was observed that the reactant adhered to the flask wall due to static electricity.
  • the hydrolysis reaction was allowed to proceed by bringing the extracted reactant into contact with moisture in the atmosphere.
  • the obtained reaction product was dried under reduced pressure at 80° C. to remove volatile compounds, and modified propylene polymer 2 was obtained.
  • the hydroxyl group content of the obtained modified propylene polymer 2 was 5.8.
  • Modified propylene polymer 2 was white.
  • Example 2 The results of Example 2 are shown in Tables 1, 2, 3 and 4.
  • Example 3 Production of modified propylene polymer 3> 10.1 g of a portion (81.1 g) of the PPZn powder obtained in Synthesis Example 2 was taken into a flask in which the gas inside was replaced with nitrogen gas, and a mixed gas of oxygen gas/nitrogen gas (oxygen Gas: 5.25 vol%, nitrogen gas: 94.75 vol%, dew point: -50.8°C) was passed from the bottom of the PPZn powder at a flow rate of 200 mL/min, and the PPZn powder and oxygen gas were heated at 30°C for 30 minutes. Made it react.
  • oxygen Gas 5.25 vol%
  • nitrogen gas 94.75 vol%
  • the flask was opened and the obtained reaction product was taken out. When taking it out, it was observed that the reactant adhered to the flask wall due to static electricity.
  • the hydrolysis reaction was allowed to proceed by bringing the extracted reactant into contact with moisture in the atmosphere.
  • the obtained reaction product was dried under reduced pressure at 80° C. to remove volatile compounds, and modified propylene polymer 3 was obtained.
  • the hydroxyl group content of the obtained modified propylene polymer 3 was 5.0.
  • Example 3 The results of Example 3 are shown in Tables 1, 2, 3 and 4.
  • Example 4 Production of modified propylene polymer 4> 20.0 g of a portion (81.1 g) of the PPZn powder obtained in Synthesis Example 2 was taken into a flask in which the gas inside was replaced with nitrogen gas, and a mixed gas of oxygen gas/nitrogen gas (oxygen Gas: 5.25 vol%, nitrogen gas: 94.75 vol%, dew point: -50.8°C) was passed from the bottom of the PPZn powder at a flow rate of 400 mL/min, and the PPZn powder and oxygen gas were reacted at 61°C for 30 minutes. I let it happen.
  • the flask was opened and the obtained reaction product was taken out. When taking it out, it was observed that the reactant adhered to the flask wall due to static electricity. A portion of the reactant taken out (3.9 g) was brought into contact with moisture in the atmosphere to advance the hydrolysis reaction. The obtained reaction product was dried under reduced pressure at 80° C. to remove volatile compounds, and modified propylene polymer 4 was obtained. The remaining reactants were used in Examples and Comparative Examples described later.
  • the hydroxyl group content of the obtained modified propylene polymer 4 was 6.6.
  • Modified propylene polymer 4 was white.
  • Example 4 The results of Example 4 are shown in Tables 1, 2, 3 and 4.
  • Example 5 Production of modified propylene polymer 5> A portion (3.8 g) of the remaining reaction product obtained in Example 4 was fractionated into a flask whose internal gas was replaced with nitrogen gas, and water-containing nitrogen gas was fractionated at a flow rate of 300 mL/min. The reactant was allowed to flow from the bottom, and hydrolysis and volatile compounds were removed at 66° C. for 300 minutes to obtain modified propylene polymer 5.
  • the flask was opened and the obtained reaction product was taken out.
  • the obtained reaction product was dried under reduced pressure at 80° C. to remove volatile compounds, and modified propylene polymer 5 was obtained.
  • the hydroxyl group content of the obtained modified propylene polymer 5 was 5.1.
  • Modified propylene polymer 5 was white.
  • Example 5 The results of Example 5 are shown in Tables 1, 2, 3 and 4.
  • Example 6 Production of modified propylene polymer 6> A portion (3.9 g) of the remaining reactant obtained in Example 4 was added to a Soxhlet extractor, and extracted with boiled water for 240 minutes to remove hydrolysis and volatile compounds. removed.
  • the flask was opened and the obtained reaction product was taken out. By drying the taken out reaction product under reduced pressure at 80° C., volatile compounds were removed, and modified propylene polymer 6 was obtained.
  • the hydroxyl group content of the obtained modified propylene polymer 6 was 7.5.
  • Modified propylene polymer 6 was white.
  • Example 6 The results of Example 6 are shown in Tables 1, 2, 3 and 4.
  • Example 7 Production of modified propylene polymer 7> A portion (3.9 g) of the remaining reactant obtained in Example 4 was added to a Soxhlet extractor, and extracted with boiling ethanol for 240 minutes to remove alcoholysis and volatile compounds. was removed.
  • the flask was opened and the obtained reaction product was taken out. By drying the taken out reaction product under reduced pressure at 80° C., volatile compounds were removed, and modified propylene polymer 7 was obtained.
  • the hydroxyl group content of the obtained modified propylene polymer 7 was 6.0.
  • Modified propylene polymer 7 was white.
  • Example 7 The results of Example 7 are shown in Tables 1, 2, 3 and 4.
  • Example 8 Production of modified propylene polymer 8> A portion (3.9 g) of the remaining reaction product obtained in Example 4 was taken into a flask, and 50 mL of toluene, 10 mL of methanol, and 10 mL of concentrated hydrochloric acid were added thereto, followed by stirring at room temperature for 60 minutes. Thus, hydrolysis was carried out. After pouring the contents into 200 mL of methanol, the solid was filtered off, and the obtained solid was washed with water and then with acetone.
  • the obtained reaction product was dried under reduced pressure at 80° C. to remove volatile compounds, and modified propylene polymer 8 was obtained.
  • Example 8 The results of Example 8 are shown in Tables 1, 2, 3 and 4.
  • the combustible gas has been removed by closing the pressure reducing valve to create a closed system after the degree of vacuum in the autoclave reaches -0.100 MPa, and maintaining the degree of vacuum at -0.100 MPa for one minute. I checked it out.
  • Example 9 Production of modified propylene polymer 9> 9.9 g of a portion (129.7 g) of the PPZn powder obtained in Synthesis Example 3 was taken into a flask in which the gas inside was replaced with nitrogen gas, and a mixed gas of oxygen gas/nitrogen gas (oxygen Gas: 0.1 vol%, nitrogen gas: 99.9 vol%) was passed from below the PPZn powder at a flow rate of 10 L/min, and the PPZn powder and oxygen gas were reacted at 63° C. for 30 minutes. Thereafter, 10 mL of degassed ethanol was added, and the mixture was allowed to stand at room temperature for 30 minutes.
  • oxygen Gas oxygen Gas: 0.1 vol%, nitrogen gas: 99.9 vol%
  • Example 9 The results of Example 9 are shown in Tables 5 and 6.
  • Example 10 Production of modified propylene polymer 10> 10.0 g of a portion (129.7 g) of the PPZn powder obtained in Synthesis Example 3 was taken into a flask in which the gas inside was replaced with nitrogen gas, and a mixed gas of oxygen gas/nitrogen gas (oxygen Gas: 1.0 vol%, nitrogen gas: 99.0 vol%) was passed from the bottom of the PPZn powder at a flow rate of 10 L/min, and the PPZn powder and oxygen gas were reacted at 64° C. for 30 minutes. Thereafter, 10 mL of degassed ethanol was added, and the mixture was allowed to stand at room temperature for 30 minutes.
  • oxygen Gas oxygen Gas: 1.0 vol%, nitrogen gas: 99.0 vol%
  • Example 10 The results of Example 10 are shown in Tables 5 and 6.
  • Example 11 Production of modified propylene polymer 11> 10.0 g of a portion (129.7 g) of the PPZn powder obtained in Synthesis Example 3 was taken into a flask in which the gas inside was replaced with nitrogen gas, and a mixed gas of oxygen gas/nitrogen gas (oxygen Gas: 5.25 vol%, nitrogen gas: 94.75 vol%) was passed from the bottom of the PPZn powder at a flow rate of 10 L/min, and the PPZn powder and oxygen gas were reacted at 69° C. for 30 minutes. Thereafter, 10 mL of degassed ethanol was added, and the mixture was allowed to stand at room temperature for 30 minutes. Thereafter, the contents were filtered and dried under reduced pressure at 80° C.
  • Example 11 The results of Example 11 are shown in Tables 5 and 6.
  • Ethylene gas was introduced until the internal pressure reached -0.052 MPa, and the ethylene gas valve was closed. As a result, the internal temperature was 7.6°C. Thereafter, 780 g of propylene was added into the autoclave, and then 7.4 mL of diethylzinc (2.05 mol/L, hexane solution) was added. Thereafter, the autoclave was heated to carry out copolymerization of propylene and ethylene at 80° C. for another 60 minutes. Thereafter, remaining flammable gases such as propylene and heptane were removed by purging propylene and ethylene and reducing the pressure inside the autoclave at 72°C.
  • the combustible gas has been removed by closing the pressure reducing valve to create a closed system after the degree of vacuum in the autoclave reaches -0.100 MPa, and maintaining the degree of vacuum at -0.100 MPa for one minute. I checked it out.
  • Example 12 Production of modified propylene/ethylene random copolymer> 10.0 g of a portion (55.2 g) of the random PPZn powder obtained in Synthesis Example 4 was taken into a flask in which the gas inside was replaced with nitrogen gas, and a mixed gas of oxygen gas/nitrogen gas ( Oxygen gas: 5.25 vol%, nitrogen gas: 94.75 vol%) was passed from the bottom of the random PPZn powder at a flow rate of 2 L/min, and the random PPZn powder and oxygen gas were reacted at 65° C. for 30 minutes. Thereafter, 10 mL of degassed ethanol was added, and the mixture was allowed to stand at room temperature for 30 minutes.
  • Oxygen gas 5.25 vol%, nitrogen gas: 94.75 vol%
  • Example 12 The results of Example 12 are shown in Tables 5 and 6.
  • O2 is used at a high concentration outside the scope of the claims of the present application, an unintended decrease in molecular weight or narrowing of the molecular weight distribution will occur, making it difficult to obtain the desired resin structure ( This can lead to a decline in quality).
  • the modified polyolefin obtained by the production method of the present invention can be used as a filler, as a compatibilizer for other resins (for example, to improve strength, heat resistance, paintability, adhesion, printability, etc.), as a grafting agent with other resins, etc.
  • Synthetic raw materials for polymers and block polymers for example, used as compatibilizers after grafting and block formation; improvements in strength, heat resistance, paintability, adhesiveness, printability, etc.
  • the terminal polar groups of the modified polyolefin obtained by the production method of the present invention are highly reactive, and the number of terminal polar groups in the chain is small, so it is thought that crosslinking gelation is unlikely to occur.
  • the modified polyolefin obtained by the production method 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. be able to.
  • molding methods such as injection molding, injection compression molding, gas-assisted molding, and extrusion molding.
  • automobile parts such as door trims, pillars, instrument panels, and bumpers.

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Abstract

La présente invention concerne un procédé de production de polyoléfine modifiée qui présente une excellente efficacité économique (en d'autres termes, il y a peu de composé de gaz réactif (oxygène gazeux)) et une excellente sécurité, et une polyoléfine modifiée obtenue qui est d'excellente qualité (fonction en tant qu'agent de compatibilité, réactivité de groupes polaires terminaux, faible degré d'odeur, etc.).　L'invention concerne un procédé de production de polyoléfine modifiée, ledit procédé comprenant une étape (1) consistant à traiter un polymère d'oléfine qui a un groupe terminal contenant un métal organique avec un gaz mixte qui contient un composé de gaz réactif et un gaz inerte, la fraction volumique du composé de gaz réactif dans le gaz mixte étant de 0,01 à 15 % en volume.
PCT/JP2023/012415 2022-03-30 2023-03-28 Procédé de production de polyoléfine modifiée WO2023190469A1 (fr)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2002302514A (ja) * 2001-04-06 2002-10-18 Idemitsu Petrochem Co Ltd 変性ポリエチレン系樹脂の製造方法、変性ポリエチレン系樹脂及びそのフィルム
JP2021515832A (ja) * 2018-03-06 2021-06-24 アジュ ユニバーシティー インダストリー−アカデミック コーオペレイション ファウンデーションＡｊｏｕ Ｕｎｉｖｅｒｓｉｔｙ Ｉｎｄｕｓｔｒｙ−Ａｃａｄｅｍｉｃ Ｃｏｏｐｅｒａｔｉｏｎ Ｆｏｕｎｄａｔｉｏｎ 対称型ポリオレフィンブロック共重合体およびその製造方法
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JP2021515832A (ja) * 2018-03-06 2021-06-24 アジュ ユニバーシティー インダストリー−アカデミック コーオペレイション ファウンデーションＡｊｏｕ Ｕｎｉｖｅｒｓｉｔｙ Ｉｎｄｕｓｔｒｙ−Ａｃａｄｅｍｉｃ Ｃｏｏｐｅｒａｔｉｏｎ Ｆｏｕｎｄａｔｉｏｎ 対称型ポリオレフィンブロック共重合体およびその製造方法
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