WO2019132523A1 - Composition de polymère, composition de résine consistant en celle-ci et procédé destiné à la préparation de la composition de polymère - Google Patents

Composition de polymère, composition de résine consistant en celle-ci et procédé destiné à la préparation de la composition de polymère Download PDF

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WO2019132523A1
WO2019132523A1 PCT/KR2018/016686 KR2018016686W WO2019132523A1 WO 2019132523 A1 WO2019132523 A1 WO 2019132523A1 KR 2018016686 W KR2018016686 W KR 2018016686W WO 2019132523 A1 WO2019132523 A1 WO 2019132523A1
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Prior art keywords
polymer
unit
alpha olefin
polymer composition
propylene
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PCT/KR2018/016686
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English (en)
Korean (ko)
Inventor
이상익
김형민
정일구
수지스수데반
어맹선
이정아
정현중
신해진
민별하나
조은향
Original Assignee
에스케이이노베이션 주식회사
에스케이종합화학 주식회사
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Priority claimed from KR1020180168668A external-priority patent/KR102623485B1/ko
Application filed by 에스케이이노베이션 주식회사, 에스케이종합화학 주식회사 filed Critical 에스케이이노베이션 주식회사
Publication of WO2019132523A1 publication Critical patent/WO2019132523A1/fr

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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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/58—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with silicon, germanium, tin, lead, antimony, bismuth or compounds thereof

Definitions

  • the present invention relates to a polymer composition, a resin composition containing the same, and a process for producing a polymer composition. More particularly, the present invention relates to a polymer composition comprising a polymer of an alpha olefin monomer, a resin composition containing the polymer composition, and a process for producing the polymer composition.
  • Polyolefin polymers have good chemical and mechanical properties while maintaining good thermoplastics and have been used in various fields.
  • a polyolefin polymer as an impact modifier is used as a dispersed phase in polypropylene to absorb shock.
  • the polyolefin polymers used as impact modifiers include ethylene-octene copolymers, ethylene-propylene copolymers, and ethylene-butylene copolymers.
  • the glass transition temperature is low, but compatibility with polypropylene is low, making it difficult to reduce the size of the dispersed phase.
  • the ethylene-propylene copolymer has excellent compatibility with polypropylene, but it is difficult to expect a low glass transition temperature. Therefore, the development of a polyolefin having excellent compatibility with polypropylene and a low glass transition temperature is required.
  • Korean Patent Laid-Open Publication No. KR10-2016-0064389 discloses a propylene resin composition and an injection-molded article produced therefrom.
  • polyolefins having excellent compatibility with propylene and having a low glass transition temperature have not been disclosed.
  • An object of the present invention is to provide a polymer composition having improved impact resistance, dispersibility and mechanical properties at low temperatures.
  • An object of the present invention is to provide a resin composition comprising a polymer composition having improved impact resistance, dispersibility and mechanical properties at low temperatures.
  • An object of the present invention is to provide a process for producing a polymer composition having improved impact resistance, dispersibility and mechanical properties at low temperatures.
  • a first polymer unit comprising a polymer of C6 to C10 alpha olefin monomers; And a second polymer unit comprising at least one of a polymer unit A comprising polypropylene and a polymer unit B comprising a copolymer of an alpha olefin monomer of C6 to C10 and propylene and having a glass transition temperature of -60 < 0 > C Or less, based on the total weight of the composition.
  • the glass transition temperature may be less than -65 ⁇ ⁇ .
  • the second polymeric unit comprises the polymeric unit B, wherein the first polymeric unit and the second polymeric unit may be present as different polymers.
  • the polymeric unit B may be a random copolymer of the C6 to C10 alpha olefin monomers with propylene.
  • the polymer dispersion index may be 10-20.
  • the second polymeric unit comprises a polymeric unit A, wherein the first polymeric unit and the second polymeric unit may be in the same polymer.
  • the first polymeric unit and the second polymeric unit may be in a double-block or multi-block.
  • the polymer dispersion index may be from 2 to 4.
  • the alpha olefin monomer may comprise at least one selected from the group consisting of 1-hexene, 1-octene, and 1-decene.
  • the alpha olefin monomer may be 1-octene.
  • the content of the first polymer unit in the total weight of the polymer composition may be 5 to 95 wt%.
  • a polypropylene and a resin composition comprising the polymer composition may be provided.
  • the resin composition may further comprise an inorganic material.
  • the inorganic material may include at least one selected from the group consisting of talc, mica, calcium carbonate, whiskers, glass fibers, asbestos, silica, ceramics, talc, clay and kaolin.
  • the resin composition may comprise 50 to 95 weight percent polypropylene, 0.1 to 30 weight percent of the polymer composition, and 0 to 40 weight percent of the inorganic material, based on the total weight of the composition.
  • the polymer composition is prepared by preparing C6 to C10 alpha olefin monomers in a reactor, polymerizing the C6 to C10 alpha olefin monomers by injecting an organometallic catalyst system into the reactor, adding propylene May be continuously injected to form a copolymer of C6-C10 alpha olefin monomer and propylene.
  • the organometallic catalyst system is selected from the group consisting of a metallocene complex, a post-metallocene complex, a half-metallocene complex, a pyridylamine complex, a phenoxyimine complex, a bis-imine pyridine- At least one selected from the group consisting of a silanediamine complex, a salen complex, a salan complex, a salarene complex, a Schiff salt mechanical complex, a dimer form of a double anionic indenoldyryl complex, and other poly chelating salt mechanical complexes can do.
  • the organometallic catalyst system may comprise a pyridine amido hafnium post-metallocene.
  • the alpha olefin monomer may be polymerized by further injecting a catalytic activator in the polymerization of the alpha olefin monomer.
  • the catalytic activator is selected from the group consisting of alkylaluminoxanes, alkyllithium compounds, Grignard reagents, alkyl tin, alkyl zinc, trifluoroborane, triarylborane, perfluorinated triarylboron and perfluorinated And triaryl aluminum.
  • the alpha olefin monomer may be polymerized by further injecting a chain shuttling agent during polymerization of the alpha olefin monomer.
  • the chain shuttling agent comprises at least one hydrocarbyl group having from 1 to 20 carbon atoms and a metal compound or metal comprising at least one metal selected from the group consisting of Groups 1, 2, 12 and 13 Complex.
  • the polymer composition comprises a first polymer unit comprising a polymer of C6-C10 alpha-olefin monomer and a second polymer unit comprising a polypropylene comprising a polymer unit A and a C6 to C10 alpha olefin And a polymer unit B comprising a copolymer of a monomer and propylene, and is excellent in compatibility or compatibility with propylene, and has a low glass transition temperature and excellent cold resistance.
  • the resin composition comprising the polymer composition may include a copolymer of an alpha olefin monomer of C6 to C10 and a copolymer of an alpha olefin monomer of C6 to C10 and propylene to improve the impact strength while maintaining excellent flexural strength .
  • the resin composition comprising the polymer composition may include a polymer of an alpha olefin monomer of C6 to C10, whereby the yield strength and elongation can be improved.
  • a polymer composition having excellent cold resistance and compatibility with polypropylene a resin composition comprising the polymer composition, and a method of producing the polymer composition.
  • polymer unit means a polymer containing molecular units such that the molecular weight can be recognized as a polymer.
  • the polymeric unit may be a polymer, and in another aspect, the polymeric unit may be present in plurality in one polymer.
  • the polymer may be a block copolymer or a random copolymer.
  • the polymer unit contained therein may be a structure representing each block or representing a plurality of blocks.
  • the polymer unit may comprise a plurality of sub-polymer units (e.g., polymer units A or B).
  • the polymer composition comprises a first polymer unit comprising a polymer of an alpha olefin monomer of C6 to C10 and a second polymer unit comprising a polypropylene comprising polymer units A and C6 to C10 alpha olefin monomers and propylene propylene), and may have a glass transition temperature of -60 ⁇ ⁇ or lower.
  • the polymer composition according to the present invention includes the first polymer unit (a polymer of an alpha olefin monomer of C6 to C10), so that the yield strength and elongation of the resin composition can be excellent.
  • the first polymer unit a polymer of an alpha olefin monomer of C6 to C10
  • the polymer composition according to the present invention can improve compatibility or miscibility between the polymer composition and the polypropylene by including the polymer unit B (a copolymer of the alpha olefin monomer and propylene of the above C6 to C10). Accordingly, the polymer composition is uniformly dispersed in the polypropylene, and the bending strength and impact strength of the resin composition containing the same can be excellent at the same time.
  • the polymer unit B a copolymer of the alpha olefin monomer and propylene of the above C6 to C10
  • the glass transition temperature of the polymer composition may be below -60 ⁇ ⁇ , preferably below -65 ⁇ ⁇ .
  • the lower limit of the glass transition temperature is not limited. For example, it may be -80 ⁇ ⁇ or higher and -90 ⁇ ⁇ or higher.
  • the above-mentioned polymer composition having a glass transition temperature range can be effectively applied to a resin composition such as a vehicle to be exposed to a severe low temperature by maintaining excellent mechanical properties and impact resistance even under a low temperature environment.
  • the second polymeric unit comprises the polymeric unit B, wherein the first polymeric unit and the second polymeric unit may be present as different polymers.
  • the first polymer unit comprises a polymer of independent C6 to C10 alpha olefin monomers
  • the second polymer unit comprises a copolymer of C6 to C10 alpha olefin monomers with propylene
  • the first polymer Unit and the second polymeric unit may be present as different polymers. That is, the polymer composition according to the present invention may comprise a blend of C6 to C10 alpha olefin polymers (first polymer unit) and C6 to C10 alpha olefin monomers and a copolymer of propylene (second polymer unit) have.
  • the second polymeric unit comprises a block copolymer, a random copolymer, and an alternating copolymer of C6 to C10 alpha olefin monomers and propylene.
  • the second polymer unit may comprise a random copolymer of C6 to C10 alpha olefin monomers with propylene.
  • the second polymeric unit of the polymer composition comprises the polymeric unit B, wherein the first polymeric unit and the second polymeric unit are present as different polymers and the polymeric unit B is a C6 to C10 Of a polymer of an alpha olefin monomer and a random copolymer of propylene, wherein the polymer composition may have a Polydispersity Index of 10 to 20. Within the range of the polymer dispersion index, the polymer composition has polymers having various weight average molecular weights and sizes, so that the impact resistance of the resin composition containing the polymer composition can be further improved.
  • the second polymeric unit comprises the polymeric unit A, and the first polymeric unit and the second polymeric unit may be present in the same polymer.
  • the polymer composition according to the present invention can be combined with a C6 to C10 alpha olefin polymer block (first polymer unit) and a polypropylene block (second polymer unit, polymer unit A) to form one polymer .
  • the first polymer unit block and the second polymer unit block may be placed in the polymer singularly or plurally so that a double block or multi Block copolymer can be formed.
  • the second polymeric unit may comprise a polypropylene and a tapered block of the C6 to C10 alpha olefin monomers.
  • the compatibility of the polymer composition and the polypropylene can be further improved.
  • compatibility with polypropylene is further improved, and the impact resistance and durability of the resin composition containing the same can be further improved.
  • the polymer composition is prepared by combining the first polymer unit comprising a polymer of the C6 to C10 alpha olefin monomers and the second polymer unit comprising polypropylene to form a mixture of propylene and C6 to C10 Alpha-olefin monomer, wherein the polymer dispersion index of the polymer composition may be from 2 to 4.
  • the polymer composition has a polymer of similar size and / or molecular weight, so that the durability and processability of the resin composition containing the same can be improved.
  • the C6 to C10 alpha olefin monomers comprise propylene and at least one alpha olefin monomer capable of performing the polymerization process.
  • the alpha olefin monomers may be selected from the group consisting of 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 5-methyl-2-norbornene, tetracyclodecene, 1,5-hexadiene, 1,4-hexadiene, 1,5-octadiene, 1,6-octadiene, Norbornene, vinyl norbornene, dicyclopentadiene, and 7-methyl-1,6-octadiene.
  • the alpha olefin monomer may include at least one selected from the group consisting of 1-hexene, 1-octene, and 1-decene, and may preferably include 1-octene.
  • the yield strength and elongation of the resin composition comprising the polymer composition can be improved.
  • the content of the first polymer unit in the total weight of the polymer composition may be about 5 to 95 wt%.
  • the first polymeric unit is present in a polymer other than the second polymeric unit, and the content of alpha olefin polymer formed by the first polymeric unit may be from about 5% to 95% by weight of the total weight of the polymeric composition have.
  • the content of the first polymer unit in the total weight of the polymer composition may be about 30 to 92 wt%, more preferably about 50 to 90 wt%.
  • the polymer composition can further improve the elongation and yield strength of the polymer while maintaining excellent compatibility with polypropylene.
  • the impact strength of the polymer composition can be further improved.
  • the content of the first polymer unit in the total weight of the polymer composition is less than about 50 wt%, the elongation and yield strength of the resin composition including the polymer composition may be lowered.
  • the content of the first polymer unit is more than about 90 wt% There is a possibility that the compatibility or the miscibility of the polymer is deteriorated.
  • the resin composition according to the present invention may comprise polypropylene and the polymer composition.
  • the polymer composition may improve compatibility or miscibility of the polypropylene by the second polymer unit.
  • the polymers in the resin composition can be evenly distributed, and the impact strength of the body with excellent bending strength can be improved.
  • the polymer composition includes the first polymer unit, so that it has excellent yield strength and elongation, and the glass transition temperature is reduced to -60 ⁇ or less, so that the cold resistance can be excellent.
  • the resin composition may further comprise inorganic materials known in the art.
  • the inorganic material may include at least one selected from the group consisting of talc, mica, calcium carbonate, whiskers, glass fibers, asbestos, silica, ceramics, talc, clay and kaolin. Accordingly, the heat resistance, moldability and durability of the resin composition can be improved.
  • the resin composition may comprise 50 to 95 weight percent polypropylene, 0.1 to 30 weight percent of the polymer composition, and 0 to 40 weight percent of the inorganic material, based on the total weight.
  • the compatibility or miscibility of the polypropylene, the polymer composition, and the inorganic material may be excellent.
  • the polymers in the resin composition are evenly distributed, and the impact resistance and cold resistance of the resin composition can be further improved.
  • the resin composition according to the exemplary embodiments has improved cold resistance, impact resistance, and elongation, and therefore can be used in automobiles, various industrial applications, architectural / civil engineering, agricultural machinery, electronic / It can be effectively applied as a reinforcing agent.
  • the polymer composition according to the present invention is prepared by preparing C6 to C10 alpha olefin monomers in a reactor, introducing an organometallic catalyst system into the reactor to polymerize the C6 to C10 alpha olefin monomers, And continuously injecting propylene into the reactor to copolymerize the C6 to C10 alpha olefin monomers with propylene.
  • the C6 to C10 alpha olefin monomers may be, for example, one or more alpha olefin monomers capable of undergoing polymerization with propylene as described above.
  • the reactor is not particularly limited as long as it can carry out the polymerization process of the C6 to C10 alpha olefin monomers with propylene.
  • the reactor may be a batch reactor, a continuous stirred tank reactor, or a tubular reactor.
  • an organometallic catalyst system may be injected into the reactor to perform the polymerization process of alpha-olefin monomer of C6 to C10 with propylene.
  • the organometallic catalyst system may be prepared by polymerizing the C6 to C10 alpha olefin monomers to form the first polymer unit, and copolymerizing the C6 to C10 alpha olefin monomers with propylene to obtain a polypropylene- It is possible to form a second polymer unit comprising at least one of the polymer unit A and the polymer unit B comprising a copolymer of the C6 to C10 alpha olefin monomers and propylene.
  • the organometallic catalyst system comprises polymerizing the C6 to C10 alpha olefin monomers to form an alpha olefin polymer, and copolymerizing the C6 to C10 alpha olefin monomer and the continuously injected propylene to form a C6 to C10 Of a copolymer of an alpha olefin and a propylene to form a composition in which an alpha olefin polymer and a copolymer of an alpha olefin and a propylene of C6 to C10 are mixed.
  • the copolymer of C6-C10 alpha olefin monomer and propylene may be any one of a block copolymer, a random copolymer and an alternating copolymer, May be a random copolymer.
  • the organometallic catalyst system forms a first polymer unit comprising a polymer of the C6 to C10 alpha olefin monomer, and subsequently polymerizing the second polymer unit to the first polymer unit,
  • the first polymer unit and the second polymer unit can be formed in the same polymer.
  • the organometallic catalyst system is selected from the group consisting of a metallocene complex, a post-metallocene complex, a half-metallocene complex, a pyridylamine complex, a phenoxyimine complex, a bis-imine pyridine- At least one selected from the group consisting of a silanediamine complex, a salen complex, a salan complex, a salarene complex, a Schiff salt mechanical complex, a dimer form of a double anionic indenoldyryl complex, and other poly chelating salt mechanical complexes , Preferably pyridine amido-halide post-metallocene, and more preferably compounds of the following formula (1).
  • the organometallic catalyst system may include at least one of a metal and a ligand system.
  • the organometallic catalyst system may comprise a Group 4 to Group 15 metal.
  • a Group 4 to 12 metal Preferably a Group 4 to 12 metal.
  • the organometallic catalyst system may comprise hafnium (Hf).
  • Hf hafnium
  • the metals may be connected by a double anionic ligand or a? -Containing ligand system.
  • the metal may have a +1, +2, +3, or +4 oxidation number, preferably a +2, +3 or +4 oxidation number, more preferably a +3 or +4 oxidation number have.
  • the ligand system may comprise a multidentate ligand system that forms a bond with the metal.
  • the multidentate ligand system may comprise a? -Terminal ligand system or an anionic ligand system.
  • the ⁇ -donor ligand system can be a conjugated diene, a non-conjugated diene, a cyclic diene, a non-conjugated diene, at least one member selected from the group consisting of dienyl, allyl, boratabenzene groups, phosphole, and arene may be included .
  • the multidentate ligand system may comprise two or more Group 15 or Group 16 elements that couple a? -Containing ligand system and are coupled to the metal.
  • the Group 15 element may include nitrogen or phosphorus
  • the Group 16 element may include oxygen or sulfur.
  • the anionic ligand system can be selected from the group consisting of cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, Indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenyl-indenyl 2-methyl-4-phenyl-indenyl, tetrahydrofluorenyl, octahydrofluorenyl, 1-indacenyl, 3-pyrrolidinoid- 3-pyrrolidinoinden-1-yl), and tetrahydroindenyl.
  • the polymerization of the alpha olefin monomer may be carried out further comprising introducing a catalytically active agent.
  • the catalyst activator can activate the organometallic catalyst system to promote the polymerization of C6 to C10 alpha olefin monomers with polypropylene.
  • the catalytic activator may be provided by providing a hydrocarbyl or hydride optionally substituted on the metal contained in the organometallic catalyst system, or by activating the catalyst by extracting any functional groups from the metal .
  • the catalyst activator may comprise an alkyl aluminum compound or a strong neutral Lewis acid.
  • the alkaluminum compound may be activated by activating the organometallic catalyst system by providing a hydrocarbyl or hydride optionally substituted on the metal contained in the organometallic catalyst system.
  • the neutral Lewis strong acid may be selected from the group consisting of trifluoro borane, triaryl borane, perflurinated triaryl boron, and perflurinated triaryl aluminum.
  • the perfluorinated triarylboron includes trispentafluorophenylborane
  • the perfluorinated triarylaluminum may include tripentafluorophenylalanine.
  • the neutral leucite may be activated by activating the organometallic catalyst system by extracting any functional group from the metal contained in the organometallic catalyst system.
  • the step of polymerizing the alpha olefin monomer can be carried out comprising injecting a chain shuttling agent.
  • the chain shuttling agent can facilitate the polymerization of the second polymeric unit subsequent to the first polymeric unit.
  • the chain shuttling agent may comprise a metal compound or metal complex comprising at least one metal selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms and groups 1, 2, 12 and 13 Preferably at least one hydrocarbyl group having at least one carbon number of 1 to 12, and at least one metal selected from the group consisting of aluminum, gallium and zinc.
  • the hydrocarbyl group may be a linear or branched alkyl group having 2 to 8 carbon atoms.
  • the chain shuttling agent may comprise a trialkylaluminum or dialkylzinc compound.
  • the chain shuttling agent may be selected from the group consisting of triethyl aluminum, tri (i-propyl) aluminum, tri (i-butyl) aluminum, Zinc, and combinations thereof.
  • a copolymer of C6-C10 alpha-olefin monomer and propylene may be prepared by continuously injecting propylene into a reactor in which polymerization of the alpha-olefin monomer of C6 to C10 has been carried out.
  • the continuous injection time of the propylene may be 1 to 20 minutes.
  • the yield of the copolymerization reaction of propylene and the alpha olefin monomer can be improved and the efficiency of the process can be improved.
  • the value of Polymer Dispersion Index (PDI) increases, and the impact strength and flexural strength of the resin composition containing the same can be excellent at the same time.
  • the polymer composition according to an exemplary embodiment can satisfy the glass transition temperature range described above. Further, in some embodiments, the polymer composition may be excellent in compatibility with, or miscibility with, polypropylene.
  • the polymer composition according to the exemplary embodiments has improved cold resistance, impact resistance, and elongation as described above, and therefore can be used in automobiles, various industries, construction / civil engineering, agricultural machinery, electronic / And the like can be effectively applied as an impact modifier.
  • the polymerization process was carried out in the same manner as in Example 1, except that the continuous injection time of propylene was 2 minutes.
  • the polymerization process was carried out in the same manner as in Example 1, except that the continuous injection time of propylene was 10 minutes.
  • Polymerization was carried out in the same manner as in Example 1, except that the continuous injection time of propylene was 15 minutes.
  • the polymerization process was carried out in the same manner as in Example 1, except that the chain shuttling agent diethylzinc was injected at a catalyst input of 300 ⁇ mol.
  • Comparative Example 1 Copolymer preparation of 1-octene and ethylene
  • Tg a weight average molecular weight (Mw), a polymer dispersion index (PDI) and the number of moles of the resulting polymer were measured for the 1-octene and ethylene copolymers of the polymer compositions of Examples 1 to 5 and Comparative Examples was measured.
  • the glass transition temperature was measured in a temperature range of -100 to 200 ° C at a rate of 10 ° C / min under a nitrogen atmosphere using a DSC instrument (Mettler Tolledo DSC822e).
  • the weight average molecular weight and polydispersity index (PDI) of PL210 were measured by PL210 GPC equipped with PL Mixed-BX2 + preCol at a rate of 1.0 mL / min at 120 ° C in tetrachloroethane solvent. Respectively.
  • Example Comparative Example 1 One 2 3 4 5 6 Tg ( ⁇ ⁇ ) -64.5 -65.9 -65.8 -66.0 -64.2 -63.1 -56 Molecular weight (Mw) 1066000 710200 164800 800000 1505000 1201000 600,000 Polymer Dispersibility Index (PDI) 15.25 10.86 13.65 18 11.65 2.5 2.0 Polymer mole number / Catalyst mole number 90 95 100 93 96 3 2.5
  • the polymer composition according to the present invention unlike Comparative Example 1, had a glass transition temperature of -60 ° C. or less.
  • Examples 1 to 4 and 6 show that the polymerized polymer It can be confirmed that the confiscation ratio is above 90.
  • the polymer compositions of Examples 1 to 4 contain a polyolefin and a copolymer of octene and propylene.
  • Examples 1 to 4 and 6 it was confirmed that the polymer dispersion index (PDI) was 10 or more. Thus, Examples 1 to 4 and 6 show that various sizes of polymer are present in the polymer composition. Thus, it can be confirmed that the first polymer unit and the second polymer unit exist as separate polymers.
  • PDI polymer dispersion index
  • Example 5 since the molar ratio of the polymerized polymer to the number of moles of the catalyst is 3, it can be confirmed that the polymerization reaction almost similar to the living polymerization in which the polymerization is continued in the state where the bond between the catalyst and the polymer is maintained. Thus, it can be confirmed that a block copolymer in which the first polymer unit and the second polymer unit are present as blocks is present in the polymer composition of Example 5.
  • Example 7 A compounding process was performed in the same manner as in Example 7, except that the polymer composition of Example 2 was injected in place of the polymer composition of Example 1.
  • Example 7 A compounding process was performed in the same manner as in Example 7, except that the polymer composition of Example 3 was injected instead of the polymer composition of Example 1.
  • Example 7 A compounding process was carried out in the same manner as in Example 7, except that the polymer composition of Example 4 was injected instead of the polymer composition of Example 1.
  • Example 7 A compounding process was carried out in the same manner as in Example 7 except that the polymer composition of Example 5 was injected instead of the polymer composition of Example 1.
  • Example 7 A compounding process was carried out in the same manner as in Example 7, except that the polymer composition of Example 6 was injected instead of the polymer composition of Example 1.
  • Example 7 The compounding process was carried out in the same manner as in Example 7, except that the polymer of 1-octene and propylene of Comparative Example 1 was used instead of the polymer composition of Example 1.
  • Yield strength and elongation were measured according to ASTM D638 standard, and the moving speed of the crosshead was 500 mm / min.
  • Example Comparative Example 2 7 8 9 10 11 12 Impact strength (kgf cm / cm) 19.2 19.8 20.1 14.2 16.1 16.4 14.3 Flexural Strength (kgf / cm 2 ) 8124 8234 8136 8380 8270 8256 8383 Yield strength (kgf / cm 2 ) 195 183 201 170 223 221 169 Elongation (%) 400 370 395 55 405 400 50
  • Examples 7 to 12 were superior in impact strength, elongation, and yield strength to each other, while maintaining excellent flexural strength.
  • Examples 7 to 11 show that the polymer dispersions It was confirmed that the impact strength was superior, including the polymer compositions of Examples 1 to 5, in which the index was 10 or more.
  • Example 12 includes the polymer composition of Example 5 having a polymer dispersion index of 2.5, which indicates that the yield strength is better.

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  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne une composition de polymère comportant une excellente résistance au froid, la composition de polymère consistant : en une première unité de polymérisation contenant un polymère de monomères d'alpha-oléfine en C6 à C10 ; et en une seconde unité de polymère consistant en une unité de polymère A contenant du polypropylène et/ou en une unité de polymère B contenant un copolymère d'un monomère d'alpha oléfine en C6 à C10 et du propylène, la composition polymère présentant une température de transition vitreuse de -60 °C ou moins.
PCT/KR2018/016686 2017-12-27 2018-12-26 Composition de polymère, composition de résine consistant en celle-ci et procédé destiné à la préparation de la composition de polymère WO2019132523A1 (fr)

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KR10-2017-0180943 2017-12-27
KR20170180943 2017-12-27
KR10-2018-0168668 2018-12-24
KR1020180168668A KR102623485B1 (ko) 2017-12-27 2018-12-24 중합체 조성물, 이를 포함하는 수지 조성물 및 중합체 조성물의 제조방법

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WO2019132523A1 true WO2019132523A1 (fr) 2019-07-04

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888949A (en) * 1973-06-21 1975-06-10 Du Pont Blends of propylene-alpha-olefin copolymers and polypropylene
KR19990071757A (ko) * 1995-11-30 1999-09-27 만셀 케이쓰 로드니 폴리프로필렌, 고급 알파-올레핀 공중합체로 제조한 제품
KR20010022830A (ko) * 1997-08-12 2001-03-26 엑손 케미칼 패턴츠 인코포레이티드 이소택틱 폴리프로필렌과 알파-올레핀/프로필렌 공중합체의 열가소성 중합체 블렌드
KR20130129188A (ko) * 2010-10-21 2013-11-27 바셀 폴리올레핀 이탈리아 에스.알.엘 부텐－１ 공중합체를 갖는 감압 접착제
KR20170067036A (ko) * 2015-12-07 2017-06-15 주식회사 엘지화학 폴리프로필렌계 복합재

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888949A (en) * 1973-06-21 1975-06-10 Du Pont Blends of propylene-alpha-olefin copolymers and polypropylene
KR19990071757A (ko) * 1995-11-30 1999-09-27 만셀 케이쓰 로드니 폴리프로필렌, 고급 알파-올레핀 공중합체로 제조한 제품
KR20010022830A (ko) * 1997-08-12 2001-03-26 엑손 케미칼 패턴츠 인코포레이티드 이소택틱 폴리프로필렌과 알파-올레핀/프로필렌 공중합체의 열가소성 중합체 블렌드
KR20130129188A (ko) * 2010-10-21 2013-11-27 바셀 폴리올레핀 이탈리아 에스.알.엘 부텐－１ 공중합체를 갖는 감압 접착제
KR20170067036A (ko) * 2015-12-07 2017-06-15 주식회사 엘지화학 폴리프로필렌계 복합재

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