WO2010032793A1 - プロピレン系ブロック共重合体、該共重合体を含む組成物およびこれらから得られる成形体 - Google Patents
プロピレン系ブロック共重合体、該共重合体を含む組成物およびこれらから得られる成形体 Download PDFInfo
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- WO2010032793A1 WO2010032793A1 PCT/JP2009/066274 JP2009066274W WO2010032793A1 WO 2010032793 A1 WO2010032793 A1 WO 2010032793A1 JP 2009066274 W JP2009066274 W JP 2009066274W WO 2010032793 A1 WO2010032793 A1 WO 2010032793A1
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- 0 CCCC(*)(C(C)C(C1(*)*)NCC)C(C)(*)C1(*)NC Chemical compound CCCC(*)(C(C)C(C1(*)*)NCC)C(C)(*)C1(*)NC 0.000 description 1
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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
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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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
- C08F297/083—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 the monomers being ethylene or propylene
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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
- 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
- C08F4/60—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 refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
Definitions
- the present invention relates to a propylene-based block copolymer, a composition containing the copolymer, and a molded product obtained therefrom.
- the present invention is a propylene-based block copolymer having an excellent balance between rigidity and impact resistance, further having good molding processability, and extremely excellent appearance characteristics at the time of molding, a composition containing the copolymer, and
- the present invention relates to a molded body obtained from this.
- Propylene-based polymers are widely used in general, such as automotive interior applications and automotive exterior applications such as fenders, bumpers, side moldings, mudguards, and mirror covers by injection molding because of their excellent rigidity, hardness, and heat resistance.
- polyethylene or rubber component amorphous or low crystalline ethylene / propylene copolymer (EPR), amorphous ethylene / ⁇ -olefin copolymer, etc. may be blended in the propylene polymer.
- EPR ethylene / propylene copolymer
- polypropylene compositions in which impact resistance is improved by direct polymerization and polypropylene compositions to which an inorganic filler such as talc is added in order to compensate for the rigidity that is lowered by the blending of rubber components.
- an inorganic filler such as talc
- rigidity- A propylene-based polymer having a further improved impact resistance balance (that is, excellent in both rigidity and impact resistance) or a composition comprising the polymer is awaited.
- a propylene-based polymer called a flow mark generated by an irregular flow of a melt generated at the time of molding, which can improve a molding appearance defect, or a composition comprising the polymer is also desired.
- a technique generally known as a means for solving such a problem is wide molecular weight distribution of a propylene polymer.
- a propylene polymer having a high molecular weight component exhibits an excellent effect.
- Patent Document 1 Japanese Patent Laid-Open No. 5-170843 (Patent Document 1)) or a catalyst containing a plurality of types of electron donors has been used.
- Patent Document 2 Japanese Patent Laid-Open No. Hei 3-7703
- Patent Document 3 Japanese Patent No. 8-120021
- Patent Document 4 a method for improving appearance characteristics while maintaining rigidity-impact resistance by mixing various propylene resin compositions
- Patent Document 5 Japanese Patent Application Laid-Open No. 47-34478
- Patent Documents 1 and 2 improve the balance of rigidity and impact resistance, but have not improved the molding appearance.
- Patent Document 3 is insufficient in improving the flow mark molding appearance, and Patent Document 4 improves the flow mark molding appearance, but the high molecular weight propylene-ethylene rubber component is agglomerated, resulting in the surface of the molded product. In some cases, a bumpy defect may occur.
- Patent Document 5 can achieve a broad molecular weight distribution by utilizing the characteristics of the catalyst, it requires a deashing step because of a large amount of residual metal due to low activity, and because the stereoregularity is extremely low, There is a problem that the rigidity cannot be increased.
- the present invention has been made in view of the prior art as described above, and can provide a highly active propylene-based polymer that is excellent in both rigidity and impact resistance and has excellent molded appearance. Furthermore, it aims at providing the composition containing this polymer, and the molded object obtained from these.
- the present invention can provide a highly active propylene-based block copolymer having high melt viscoelasticity, excellent balance between rigidity and impact resistance, good moldability, and extremely excellent molded appearance, It is an object of the present invention to provide a composition containing the copolymer and a molded product obtained therefrom.
- “Wide molecular weight distribution co-polymer” consisting of propylene having a specific property and one or more olefins selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms, which are insoluble in decane (corresponding to Dinsol)
- Propylene-based block copolymer containing “unified rubber” corresponding to a portion soluble in n-decane at room temperature (Dsol)
- Dsol room temperature
- the propylene-based block copolymer has a very good molding appearance and rigidity-impact resistance with higher order of properties and high molecular weight components of Dsol. It found that moldings excellent in balance of sex can be obtained, and have completed the present invention.
- the propylene block copolymer of the present invention is composed of 5 to 80% by weight of a part soluble in room temperature n-decane (Dsol) and 20 to 95% by weight of a part insoluble in room temperature n-decane (Dinsol). (However, the total amount of Dsol and Dinsol is 100% by weight), which is characterized by satisfying the following requirements [1] to [3] simultaneously.
- the molecular weight distribution (Mw / Mn) of Dsol is 7.0 or more and 30 or less
- Dinsol molecular weight distribution (Mw / Mn) is 7.0 or more and 30 or less
- Mz / Mw is 6.0 or more and 20 or less
- the pentad fraction (mmmm) of Dinsol is 93% or more.
- the propylene-based block copolymer is characterized by satisfying the following requirements [4] and [5] in addition to the above requirements [1] to [3].
- the intrinsic viscosity [ ⁇ ] (dl / g) of Dsol is 1.5 or more and 10.0 or less
- [5] Mz / Mn of Dinsol is 70 or more and 300 or less.
- the room temperature n-decane soluble part is composed mainly of a copolymer rubber composed of propylene and one or more olefins selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms.
- the room temperature n-decane-insoluble portion (Dinsol) is composed of 98.5 to 100 mol% of propylene and 0 to 1.5 mol% of one or more olefins selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms.
- a crystalline propylene-based (co) polymer consisting of
- the step of producing the copolymer rubber is characterized by polymerizing propylene and one or more olefins selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms in one step.
- the propylene-based block copolymer includes titanium, magnesium, halogen and a cyclic ester compound (a) specified by the following formula (1) and a cyclic ester compound (b) specified by the following formula (2).
- n is an integer of 5 to 10.
- R 2 and R 3 are each independently COOR 1 or R, and at least one of R 2 and R 3 is COOR 1 .
- a single bond in the cyclic skeleton (C—C b bond, C a —C b bond when R 3 is COOR 1 and C—C bond (when n is 6 to 10)) is a double bond. It may be replaced.
- R 1 is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- a plurality of Rs are each independently an atom selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group.
- a double bond may be included in the ring skeleton formed by bonding R to each other, and when the ring skeleton includes two or more C a to which COOR 1 is bonded, The number of carbon atoms forming the skeleton is 5 to 10.
- n is an integer of 5 to 10.
- R 4 and R 5 are each independently COOR 1 or a hydrogen atom, and at least one of R 4 and R 5 is COOR 1 .
- R 1 is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- a single bond in the cyclic skeleton (C—C b bond, C a —C b bond when R 5 is COOR 1 and C—C bond (when n is 6 to 10)) is a double bond. It may be replaced.
- cyclic ester compound (a) is represented by the following formula (1a) and the cyclic ester compound (b) is represented by the following formula (2a).
- n is an integer of 5 to 10.
- C—C bonds (when n is 6 to 10), C a —C bonds and C b —C bonds) in the cyclic skeleton may be replaced by double bonds.
- R 1 is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- a plurality of Rs are each independently an atom selected from a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group.
- a double bond may be included in the ring skeleton formed by bonding R to each other, and when the ring skeleton includes two or more C a to which COOR 1 is bonded, The number of carbon atoms forming the skeleton is 5 to 10.
- n is an integer of 5 to 10.
- R 1 is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. Single bonds (C—C bonds (when n is 6 to 10), C a —C bonds and C b —C bonds) in the cyclic skeleton may be replaced by double bonds.
- the present invention is characterized by a propylene resin composition comprising the propylene-based block copolymer and an inorganic filler and / or an elastomer.
- the present invention is characterized by a molded body comprising the propylene-based block copolymer.
- the propylene-based block copolymer of the present invention has a high melt elasticity due to the ultrahigh molecular weight rubber component contained in a trace amount in the wide molecular weight distribution copolymer rubber even if the flowability of the wide molecular weight distribution propylene polymer is increased. As a result, the flow in the mold at the time of injection molding can be stabilized, and the flow mark is hardly generated. At the same time, since it is not necessary to increase the molecular weight of the entire wide molecular weight distribution copolymer rubber in order to improve the flow mark generation, there is an effect that there are few appearance defects such as fish eyes and butts on the surface of the molded product.
- the propylene-based block copolymer of the present invention has a wide molecular weight distribution copolymer rubber containing a high molecular weight rubber component as a structural unit, the glass transition temperature becomes low. From the said characteristic, the propylene-type block copolymer concerning this invention has the effect of having favorable low-temperature impact property.
- the propylene-based block copolymer of the present invention has the effect of high rigidity without impairing impact resistance by orientation crystallization of a wide molecular weight distribution propylene polymer having high stereoregularity and wide molecular weight distribution.
- the propylene-based block copolymer of the present invention has a high stereoregularity and a low molecular expansion coefficient in the injection molded product due to the orientation crystallization of the wide molecular weight distribution propylene polymer, and the dimensional accuracy of the injection molded product is high. It has the effect.
- a composition containing the copolymer and a molded product obtained therefrom are various molded products having excellent characteristics, particularly automobiles. It can be used as a material for large-sized injection molding applications such as interior and exterior products and home appliance parts.
- the propylene-based block copolymer of the present invention comprises a room temperature n-decane soluble part (Dsol) of 5 to 80% by weight, preferably 10 to 50% by weight, more preferably 10 to 30% by weight, and room temperature n-decane.
- Insoluble portion (Dinsol) is composed of 20 to 95% by weight, preferably 50 to 90% by weight, more preferably 70 to 90% by weight [provided that the total amount of Dsol and Dinsol is 100% by weight].
- n-decane is composed mainly of propylene-based copolymer rubber composed of propylene and one or more olefins selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms (50 Greater than wt%, preferably 80-100 wt%, more preferably 90-100 wt%).
- One or more olefins selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms contained in the propylene copolymer rubber have a higher content than the olefins contained in the propylene polymer described later.
- the portion insoluble in room temperature n-decane (Dinsol) comprises a crystalline propylene-based (co) polymer as a main component (greater than 50% by weight, preferably 80 to 100% by weight, more preferably 90 to 100% by weight).
- the crystalline propylene-based (co) polymer contains a crystalline propylene homopolymer or 1.5 mol% or less of propylene and one or more olefins selected from ethylene and an ⁇ -olefin having 4 to 20 carbon atoms.
- a crystalline propylene copolymer is shown.
- the propylene-based block copolymer according to the present invention is characterized in that requirements [1] to [3] described later are satisfied at the same time, and more preferably, requirements [4] and / or [5] are also satisfied.
- “parts soluble in n-decane at room temperature (Dsol)” are 2 parts of propylene block copolymers at 150 ° C. in n-decane. The portion dissolved on the n-decane solution side after the temperature is lowered to 23 ° C. after dissolution by heating for a time is shown.
- n-decane soluble part a part insoluble in room temperature n-decane insoluble part
- the propylene-based block copolymer of the present invention comprises a skeleton derived from propylene and an skeleton derived from one or more olefins selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms.
- olefins selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms.
- the ⁇ -olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, -Hexadecene, 1-octadecene, 1-eicosene and the like.
- olefin constituting the skeleton resulting from one or more olefins selected from ethylene and an ⁇ -olefin having 4 to 20 carbon atoms in the copolymer ethylene or an ⁇ -olefin having 4 to 10 carbon atoms is preferable. More preferred are ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, and more preferably one or more.
- the molecular weight distribution (Mw / Mn) of Dsol is 7.0 or more and 30 or less.
- the pentad fraction (mmmm) of Dinsol is 93% or more.
- the intrinsic viscosity [ ⁇ ] (dl / g) of Dsol is 1.5 or more and 10.0 or less.
- Mz / Mn of Dinsol is 70 or more and 300 or less.
- the decane soluble part (Dsol) of the propylene-based block copolymer according to the present invention is a ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined from the measured value by gel permeation chromatography (GPC).
- Mw weight average molecular weight
- Mn number average molecular weight
- the propylene-based block copolymer of the present invention has a feature that it contains a large amount of a high-molecular-weight copolymer rubber component because Mw / Mn of the decane-soluble part (Dsol) is high. Due to such characteristics, the propylene block copolymer of the present invention can increase the melt elasticity by the high molecular weight copolymer rubber component even if the MFR of the wide molecular weight distribution propylene polymer is high. This is advantageous in achieving both fluidity and high melt tension.
- This requirement [1] can be obtained by copolymerizing propylene with one or more olefins selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms in the presence of an olefin polymerization catalyst described later. it can.
- the requirement [1] can be achieved by setting the number of polymerization stages to a plurality of stages even with an existing olefin polymerization catalyst.
- the olefin polymerization catalyst described later is used.
- the obtained copolymer rubber component does not aggregate in the propylene-based block copolymer and is easily finely dispersed.
- the polymer production apparatus can be made simpler, which is advantageous from the viewpoint of economy and energy saving.
- “one-stage polymerization” refers to a state in which the process for producing the copolymer rubber is constituted by one reactor and the polymerization conditions are not changed at all in the reactor.
- the decane insoluble part (Dinsol) of the propylene-based block copolymer according to the present invention has an Mw / Mn value of 7.0 to 30 determined from a measured value by gel permeation chromatography (GPC), From the viewpoint of maintaining impact resistance, it is preferably 7.0 to 20, and more preferably 8.0 to 18.
- the decane insoluble part (Dinsol) of the propylene-based block copolymer according to the present invention has an Mz / Mw value obtained from a measured value by GPC of 6 to 20, preferably 6.5 to 18, more Preferably, it is 7-15.
- the decane insoluble part (Dinsol) of the propylene-based block copolymer according to the present invention has a high Mw / Mn value, and thus exhibits a sufficiently wide molecular weight distribution, and is excellent in moldability and rigidity. Moreover, since the propylene-type block copolymer which concerns on this invention shows high Mz / Mw value as mentioned above, it contains many high molecular weight components, its melt tension (MT) is high and it is excellent in a moldability.
- the decane-insoluble part (Dinsol) of the propylene-based block copolymer according to the present invention as described above can be produced by multi-stage polymerization or mixing of plural types of polypropylene, but is obtained by one-stage polymerization. It is preferable.
- the decane insoluble part (Dinsol) of the propylene-based block copolymer according to the present invention is obtained by one-stage polymerization, the polymer production apparatus can be made simpler and economical.
- the high molecular weight component in the system block copolymer is preferable because it does not aggregate and becomes finely dispersed.
- the decane insoluble part (Dinsol) of the propylene-based block copolymer of the present invention has a high Mw / Mn value and a large amount of a high molecular weight component having a high Mz / Mw value, and preferably a high Mz / Mn value described later. Therefore, the high molecular weight component in the propylene-based block copolymer acts as a nucleating agent at the time of molding, and a molded product with a high degree of crystallinity can be obtained without adding a nucleating agent such as filler powder or resin powder. May be obtained.
- the high molecular weight material is finely dispersed because the action of a nucleating agent tends to increase.
- propylene is 98.5 to 100 mol%, and one or more olefins selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms are used. 0.5 mol% can be obtained by (co) polymerization.
- the pentad fraction (mmmm) of the decane insoluble part (Dinsol) of the propylene-based block copolymer of the present invention is 93% or more, preferably 94% or more, and more preferably 95% or more.
- the upper limit of the pentad fraction is 100%, preferably 99.8%, more preferably 99.5%. If the pentad fraction (mmmm) is less than 93%, the rigidity is lowered, and there is a field in which heat resistance cannot ensure the required characteristics in the product field such as a film.
- a propylene polymer polymerized with a titanium trichloride catalyst has an effect of wide molecular weight distribution as described in Patent Document 5 described above, but the pentad fraction in the decane insoluble portion is about 91 to 92%. Therefore, it cannot be used for injection molding applications that require high rigidity such as automobile materials.
- the requirement [3] is satisfied because the cyclic ester compound (a) and the cyclic ester compound (b) are contained as electron donors in the olefin polymerization catalyst described later.
- the intrinsic viscosity [ ⁇ ] (dl / g) of the decane-soluble part (Dsol) of the propylene-based block copolymer of the present invention is usually 1.5 to 10.0, impact resistance, high fluidity, and high melt elasticity. From the viewpoint of optimizing the balance, the range is preferably 2.0 to 7.0, more preferably 2.5 to 4.0. If the intrinsic viscosity [ ⁇ ] (dl / g) is lower than 1.5 dl / g, the impact resistance of the propylene-based block copolymer may be lowered, which is not preferable.
- the Mz / Mn value of the decane insoluble part (Dinsol) of the polypropylene polymer according to the present invention is 70 to 300, preferably 100 to 250, more preferably 120 to 200.
- Polypropylene with a high Mz / Mw value represents a high content ratio of components having a high molecular weight, and is expected to have a high melt tension and a high possibility of excellent moldability and rigidity.
- a propylene polymer polymerized with a titanium trichloride catalyst has an effect of wide molecular weight distribution as described in Patent Document 5 described above, but wide molecular weight distribution. This is largely due to the increase in the low molecular weight polymer, and therefore the Mz / Mn value of the propylene polymer polymerized with the titanium trichloride catalyst is only about 40 at most. Therefore, it is not suitable for the effects of having a high molecular weight polymer as in the present invention, that is, injection molding applications that require high rigidity such as automobile materials.
- a propylene-based block copolymer characterized by satisfying the above requirements [1] to [3] and more preferably satisfying the requirements [4] and [5] is produced using the following olefin polymerization catalyst. It is preferred that
- the propylene-based block copolymer according to the present invention comprises a solid titanium catalyst component (I), an organometallic compound (II) containing a metal atom selected from Group 1, Group 2 and Group 13 of the periodic table;
- the polymer is preferably obtained by polymerization in the presence of an olefin polymerization catalyst containing an electron donor (III) as necessary.
- an olefin polymerization catalyst containing an electron donor (III) as necessary.
- Solid titanium catalyst component (I) The solid titanium catalyst component (I) according to the present invention comprises titanium, magnesium, halogen and a cyclic ester compound (a) specified by the following formula (1) and a cyclic ester compound (b) specified by the following formula (2). )including.
- the cyclic ester compound (a) has a plurality of carboxylic acid ester groups and is represented by the following formula (1).
- n is an integer of 5 to 10, preferably an integer of 5 to 7, particularly preferably 6.
- C a and C b represent carbon atoms.
- R 2 and R 3 are each independently COOR 1 or R, and at least one of R 2 and R 3 is COOR 1 .
- the carbon-carbon bonds in the cyclic skeleton are preferably all single bonds, but in the cyclic skeleton, other than the C a -C a bond and the C a -C b bond when R 3 is R, Any single bond may be replaced with a double bond. That is, the C—C b bond in the cyclic skeleton, the C a —C b bond when R 3 is COOR 1 and the C—C bond (when n is 6 to 10) are replaced with double bonds. It may be done.
- a plurality of R 1 are each independently a monovalent carbon atom having 1 to 20, preferably 1 to 10, more preferably 2 to 8, more preferably 4 to 8, particularly preferably 4 to 6 carbon atoms. It is a hydrogen group.
- the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, Tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and the like.
- n-butyl group, isobutyl group, hexyl group and octyl group are preferable, and n-butyl group and isobutyl group are propylene type having wide molecular weight distribution.
- the block copolymer is particularly preferable because it can be produced.
- Plural Rs are each independently an atom selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. Or a group, but at least one R is not a hydrogen atom.
- R other than a hydrogen atom is preferably a hydrocarbon group having 1 to 20 carbon atoms.
- the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso group.
- Aliphatic hydrocarbon groups such as -propyl, n-butyl, iso-butyl, sec-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, vinyl, phenyl, octyl , An alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
- an aliphatic hydrocarbon group is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and a sec-butyl group are preferable.
- R may be bonded to each other to form a ring, and the ring skeleton formed by bonding R to each other may contain a double bond, and the ring skeleton
- the number of carbon atoms constituting the skeleton of the ring is 5 to 10.
- ring skeleton examples include a norbornane skeleton and a tetracyclododecene skeleton.
- a plurality of R may be a carbonyl structure-containing group such as a carboxylic acid ester group, an alkoxy group, a siloxy group, an aldehyde group or an acetyl group, and these substituents include carbon atoms having 1 to 20 carbon atoms. It preferably contains one or more hydrogen groups.
- Such a cyclic ester compound (a) is described in International Publication No. 2006/077945 pamphlet.
- the compound having a diester structure as described above has isomers such as cis and trans derived from a plurality of COOR 1 groups in the formula (1), and any structure meets the object of the present invention. Although it has an effect, it is preferable that the trans isomer content is higher. The higher the content of the trans isomer, the higher the activity and the stereoregularity of the resulting polymer, as well as the effect of broadening the molecular weight distribution.
- the cyclic ester compound (a) is preferably a compound represented by the following formulas (1-1) to (1-6).
- the single bond (excluding the C a -C a bond) in the cyclic skeleton may be replaced with a double bond.
- n is an integer of 7 to 10.
- a compound represented by the following formula (1a) is particularly preferable.
- [N, R 1 and R in the formula (1a) are the same as defined in the formula (1), except for a single bond in the cyclic skeleton (except for a C a -C a bond and a C a -C b bond). .) May be replaced by a double bond. That is, the C—C bond (when n is 6 to 10), the C a —C bond and the C b —C bond in the cyclic skeleton may be replaced with a double bond.
- the cyclic ester compound (a) having a diester structure as described above has isomers such as cis and trans, and any structure has an effect meeting the object of the present invention. Higher rates are particularly preferred because they tend to have higher activity and stereoregularity of the resulting polymer, as well as the effect of broadening the molecular weight distribution.
- the ratio of the trans form of the cis form and the trans form is preferably 51% or more. A more preferred lower limit is 55%, even more preferred is 60%, and particularly preferred is 65%. On the other hand, the preferable upper limit is 100%, more preferably 90%, still more preferably 85%, and particularly preferably 79%.
- the cyclic ester compound (b) has a plurality of carboxylic acid ester groups and is represented by the following formula (2).
- n is an integer of 5 to 10, preferably an integer of 5 to 7, particularly preferably 6.
- C a and C b represent carbon atoms.
- the carbon-carbon bonds in the cyclic skeleton are preferably all single bonds, but other than the C a -C a bond and the C a -C b bond in the case where R 5 is a hydrogen atom in the cyclic skeleton. Any single bond may be replaced with a double bond. That is, the C—C b bond, the C a —C b bond when R 5 is COOR 1 and the C—C bond (when n is 6 to 10) in the cyclic skeleton are replaced with double bonds. It may be done.
- R 4 and R 5 are each independently COOR 1 or a hydrogen atom, at least one of R 4 and R 5 is COOR 1 , and R 1 is each independently 1 to 20 carbon atoms. Valent hydrocarbon group.
- a plurality of R 1 are each independently a monovalent carbon atom having 1 to 20, preferably 1 to 10, more preferably 2 to 8, more preferably 4 to 8, particularly preferably 4 to 6 carbon atoms. It is a hydrogen group.
- the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, Tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and the like.
- n-butyl group, isobutyl group, hexyl group and octyl group are preferable, and n-butyl group and isobutyl group are propylene type having wide molecular weight distribution.
- the block copolymer is particularly preferable because it can be produced.
- Cyclohexane-1,2-dicarboxylate Cyclohexane-1,2-dicarboxylate di-n-propyl, Cyclohexane-1,2-dicarboxylate diisopropyl, Cyclohexane-1,2-dicarboxylate di-n-butyl, Cyclohexane-1,2-dicarboxylate diisobutyl, Cyclohexan-1,2-dicarboxylic acid dihexyl, Cyclohexane-1,2-dicarboxylate diheptyl, Dioctyl cyclohexane-1,2-dicarboxylate, Cyclohexane-1,2-dicarboxylate di-2-ethylhexyl, Didecyl cyclohexane-1,2-dicarboxylate, Cyclohexane-1,3-dicarboxylate diethyl, Cyclohexane-1,3-dicarboxylate
- Cyclohexane-1,2-diacetate Cyclohexane-1,2-dibutanate
- Cyclohexane-1,2-dibenzoate Cyclohexane-1,2-ditoluate, Etc.
- isomers such as cis and trans exist, but any structure has an effect that meets the object of the present invention.
- the ratio of the trans form of the cis form and the trans form is preferably 51% or more.
- a more preferred lower limit is 55%, even more preferred is 60%, and particularly preferred is 65%.
- the preferable upper limit is 100%, more preferably 90%, still more preferably 85%, and particularly preferably 79%. The reason for this is unknown, but it is presumed that the variation of the stereoisomer described later is in a region suitable for wide molecular weight distribution.
- the trans purity is less than 51%, the effect of wide molecular weight distribution, activity, stereospecificity and the like may be insufficient. On the other hand, if the trans purity exceeds 79%, the effect of wide molecular weight distribution may be insufficient. That is, if the trans purity is within the above range, it is advantageous to achieve both a high level of both the effect of broadening the molecular weight distribution of the polymer obtained and the activity of the catalyst and the high stereoregularity of the polymer obtained. There are many.
- the cyclic ester compound (b) is particularly preferably a compound having a cycloalkane-1,2-dicarboxylic acid diester structure or a cycloalkene-1,2-dicarboxylic acid diester structure represented by the following formula (2a).
- n and R 1 are the same as described above (that is, as defined in the formula (2)), and a single bond (provided that the C a -C a bond and the C a -C The b bond is excluded, that is, the C—C a bond, the C—C b bond and the C—C bond (when n is 6 to 10)) may be replaced with double bonds.
- Cyclohexane-1,2-dicarboxylate di-n-butyl Cyclohexane-1,2-dicarboxylate diisobutyl
- Cyclohexan-1,2-dicarboxylic acid dihexyl Cyclohexane-1,2-dicarboxylate diheptyl
- Dioctyl cyclohexane-1,2-dicarboxylate Cyclohexane-1,2-dicarboxylate di-2-ethylhexyl
- Cyclopentane-1,2-dicarboxylate diisobutyl Cycloheptane-1,2-dicarboxylate diheptyl, Diisobutyl cycloheptane-1,2-dicarboxylate, And cycloheptane-1,2-dicarboxylic acid diheptyl.
- Cyclohexane-1,2-dicarboxylate diisobutyl Cyclohexan-1,2-dicarboxylic acid dihexyl
- Cyclohexane-1,2-dicarboxylate diheptyl Dioctyl cyclohexane-1,2-dicarboxylate
- Cyclohexane-1,2-dicarboxylate di-2-ethylhexyl Is more preferable.
- the reason is not only the catalyst performance, but also that these compounds can be produced relatively inexpensively using the Diels Alder reaction.
- the cyclic ester compounds (a) and (b) may be used alone or in combination of two or more.
- the combined molar ratio of the cyclic ester compound (a) and the cyclic ester compound (b) is 10 mol. % Or more is preferable. More preferably, it is 30 mol% or more, particularly preferably 40 mol% or more, and particularly preferably 50 mol%. A preferred upper limit is 99 mol%, preferably 90 mol%. More preferably, it is 85 mol%, Most preferably, it is 80 mol%.
- the solid titanium catalyst component (I) of the present invention has a low content of the cyclic ester compound (a) of the solid titanium catalyst component (I) under conditions of a wide range of combined molar ratios of the cyclic ester compound (a).
- an olefin polymer having a very wide molecular weight distribution can be provided. The cause of this effect is unknown, but the present inventors presume as follows.
- the cyclic ester compound (a) has a very large number of steric structural variations that can be formed compared to the cyclic ester compound (b) due to the presence of the substituent R. For this reason, the influence of the cyclic ester compound (a) is dominant on the molecular weight distribution, and it is considered that an olefin polymer having an extremely wide molecular weight distribution can be provided even if the combination molar ratio is low.
- the cyclic ester compound (a) and the cyclic ester compound (b) have relatively similar structures, the basic performances such as activity and stereoregularity are unlikely to affect the effect of each other compound (the structure is When different compounds are used, there are many examples in which the activity, stereoregularity, etc. change drastically, and the effect of one compound becomes dominant.
- the solid titanium catalyst component (I) used in the present invention gives an olefin polymer having a very wide molecular weight distribution and high stereoregularity with high activity even if the content of the cyclic ester compound (a) is low. be able to.
- the propylene block copolymer of the present invention is a polymer having a wide molecular weight distribution. The reason for this is currently unknown, but the following causes are presumed.
- the cyclic hydrocarbon structure forms various three-dimensional structures such as a chair type and a boat type. Furthermore, if the cyclic structure has a substituent, the possible three-dimensional structure variations are further increased. Further, of the carbon atoms forming the cyclic skeleton of the cyclic ester compounds, the bond between the ester group (COOR 1 group) carbon atom is bonded with an ester group (COOR 1 group) other carbon atoms bound If it is a single bond, the variation of the solid structure which can be taken spreads. The ability to take such a variety of three-dimensional structures leads to the formation of a variety of active species on the solid titanium catalyst component (I).
- olefin polymers having various molecular weights can be produced at the same time, that is, a propylene block copolymer having a wide molecular weight distribution is produced. can do.
- the cyclic ester compounds (a) and (b) may be formed in the process of preparing the solid titanium catalyst component (I).
- a step in which the carboxylic anhydride or carboxylic acid dihalide corresponding to the cyclic ester compounds (a) and (b) substantially contacts with the corresponding alcohol By providing, the cyclic ester compounds (a) and (b) can be contained in the solid titanium catalyst component.
- a magnesium compound and a titanium compound are used in addition to the cyclic ester compounds (a) and (b). Moreover, unless the objective of this invention is impaired, you may use it combining the catalyst component (c) and catalyst component (d) which are mentioned later.
- Magnesium halides such as magnesium chloride and magnesium bromide
- Alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, phenoxy magnesium chloride
- Alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, 2-ethylhexoxymagnesium
- Aryloxymagnesium such as phenoxymagnesium
- Known magnesium compounds such as magnesium carboxylates such as magnesium stearate can be mentioned.
- These magnesium compounds may be used alone or in combination of two or more. These magnesium compounds may be complex compounds with other metals, double compounds, or mixtures with other metal compounds.
- a magnesium compound containing a halogen is preferable, and a magnesium halide, particularly magnesium chloride is preferably used.
- alkoxymagnesium such as ethoxymagnesium is also preferably used.
- the magnesium compound may be derived from other substances, for example, obtained by contacting an organic magnesium compound such as a Grignard reagent with a halogenated titanium, a halogenated silicon, a halogenated alcohol, or the like. Good.
- an organic magnesium compound such as a Grignard reagent with a halogenated titanium, a halogenated silicon, a halogenated alcohol, or the like.
- silicon tetrachloride as a halogenating agent
- titanium compounds include general formulas; Ti (OR) g X 4-g (R is a hydrocarbon group, X is a halogen atom, and g is 0 ⁇ g ⁇ 4.)
- R is a hydrocarbon group
- X is a halogen atom
- g is 0 ⁇ g ⁇ 4.
- Titanium tetrahalides such as TiCl 4 and TiBr 4 ; Ti (OCH 3 ) Cl 3 , Ti (OC 2 H 5 ) Cl 3 , Ti (On—C 4 H 9 ) Cl 3 , Ti (OC 2 H 5 ) Br 3 , Ti (O—isoC 4 H 9) ) Trihalogenated alkoxy titaniums such as Br 3 ; Dihalogenated alkoxytitanium such as Ti (OCH 3 ) 2 Cl 2 , Ti (OC 2 H 5 ) 2 Cl 2 ; Monohalogenated alkoxytitanium such as Ti (OCH 3 ) 3 Cl, Ti (On-C 4 H 9 ) 3 Cl, Ti (OC 2 H 5 ) 3 Br; Examples thereof include tetraalkoxytitanium such as Ti (OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 , Ti (OC 4 H 9 ) 4 , and Ti (O-2-ethylhexyl) 4 .
- titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable.
- These titanium compounds may be used alone or in combination of two or more.
- magnesium compound and titanium compound as described above may include compounds described in detail in Patent Document 1, Patent Document 2, and the like.
- the solid titanium catalyst component (I) of the present invention a known method can be used without limitation except that the cyclic ester compounds (a) and (b) are used.
- Specific preferred methods include, for example, the following methods (P-1) to (P-4).
- a solid adduct comprising a magnesium compound and a catalyst component (c), a cyclic ester compound (a) and (b), and a liquid titanium compound are suspended in the presence of an inert hydrocarbon solvent. Method to contact in turbid state.
- a solid adduct comprising a magnesium compound and a catalyst component (c), cyclic ester compounds (a) and (b), and a titanium compound in a liquid state are suspended in the presence of an inert hydrocarbon solvent. The method of making it contact in a cloudy state, and making it contact in several steps.
- a preferable reaction temperature in the preparation of the solid titanium catalyst component (I) is in the range of ⁇ 30 ° C. to 150 ° C., more preferably ⁇ 25 ° C. to 140 ° C., and further preferably ⁇ 25 to 130 ° C.
- the production of the above solid titanium catalyst component can also be carried out in the presence of a known medium, if necessary.
- this medium include aromatic hydrocarbons such as slightly polar toluene and known aliphatic hydrocarbons such as heptane, hexane, octane, decane, and cyclohexane, and alicyclic hydrocarbon compounds.
- aromatic hydrocarbons such as slightly polar toluene and known aliphatic hydrocarbons such as heptane, hexane, octane, decane, and cyclohexane
- Aliphatic hydrocarbons are preferred examples.
- Catalyst component (c) As the catalyst component (c) used for forming the solid adduct or the magnesium compound in the liquid state, a known compound that can solubilize the magnesium compound in a temperature range of room temperature to about 300 ° C. is preferable. Aldehydes, amines, carboxylic acids and mixtures thereof are preferred. Examples of these compounds include compounds described in detail in Patent Document 1 and Patent Document 2.
- Aliphatic alcohols such as methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol; Cycloaliphatic alcohols such as cyclohexanol and methylcyclohexanol; Aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol; Examples thereof include aliphatic alcohols having an alkoxy group such as n-butyl cellosolve.
- carboxylic acid examples include organic carboxylic acids having 7 or more carbon atoms such as caprylic acid and 2-ethylhexanoic acid.
- aldehydes examples include aldehydes having 7 or more carbon atoms such as capric aldehyde and 2-ethylhexyl aldehyde.
- amines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, laurylamine, 2-ethylhexylamine.
- the above alcohols are preferable, and ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol and the like are particularly preferable.
- the amount of the magnesium compound and catalyst component (c) used in preparing the solid adduct or liquid magnesium compound varies depending on the type, contact conditions, and the like. It is used in an amount of 0.1 to 20 mol / liter, preferably 0.5 to 5 mol / liter per unit volume of c). Further, if necessary, a medium inert to the solid adduct can be used in combination. As said medium, well-known hydrocarbon compounds, such as heptane, hexane, octane, decane, are mentioned as a preferable example.
- the composition ratio of magnesium to the catalyst component (c) in the solid adduct or liquid magnesium compound obtained varies depending on the type of compound used, but cannot be specified unconditionally, but with respect to 1 mol of magnesium in the magnesium compound.
- the catalyst component (c) is preferably in the range of 2.0 mol or more, more preferably 2.2 mol or more, further preferably 2.3 mol or more, particularly preferably 2.4 mol or more and 5 mol or less. .
- the solid titanium catalyst component (I) of the present invention further includes an aromatic carboxylic acid ester and / or a compound having two or more ether bonds via a plurality of carbon atoms (hereinafter also referred to as “catalyst component (d)”). .) May be included.
- the catalyst activity may be improved, the stereoregularity may be increased, or the molecular weight distribution may be further broadened.
- catalyst component (d) known aromatic carboxylic acid esters and polyether compounds that are preferably used in conventional olefin polymerization catalysts, such as those described in Patent Document 1 and Japanese Patent Application Laid-Open No. 2001-354714, are listed.
- the compound can be used without limitation.
- aromatic carboxylic acid ester examples include aromatic carboxylic acid monoesters such as benzoic acid esters (such as ethyl benzoate) and toluic acid esters, and aromatic polyvalent carboxylic acid esters such as phthalic acid esters. Can be mentioned. Among these, aromatic polycarboxylic acid esters are preferable, and phthalic acid esters are more preferable. As the phthalates, phthalic acid alkyl esters such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate and heptyl phthalate are preferable, and diisobutyl phthalate is particularly preferable.
- examples of the polyether compound include compounds represented by the following formula (3).
- m is an integer of 1 to 10, more preferably an integer of 3 to 10, and particularly preferably 3 to 5.
- R 11 , R 12 , R 31 to R 36 are each independently at least one selected from a hydrogen atom or carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron and silicon. A substituent having a seed element.
- R 11 and R 12 are preferably hydrocarbon groups having 1 to 10 carbon atoms, preferably hydrocarbon groups having 2 to 6 carbon atoms, and R 31 to R 36 are preferably hydrogen atoms or carbon atoms. It is a hydrocarbon group of the number 1-6.
- R 11 and R 12 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2 -Ethylhexyl group, decyl group, cyclopentyl group, cyclohexyl group can be mentioned, and ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group are preferable.
- R 31 to R 36 include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group, preferably a hydrogen atom and a methyl group.
- R 11 , R 12 , R 31 to R 36 preferably R 11 and R 12 may jointly form a ring other than a benzene ring, and atoms other than carbon are contained in the main chain. May be.
- 1,3-diethers are preferred, and in particular, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl.
- 1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane are preferred.
- the above cyclic ester compounds (a) and (b), the catalyst component (c), and the catalyst component (d) may be considered to belong to a component called an electron donor among those skilled in the art.
- the above-mentioned electron donor component has the effect of increasing the stereoregularity of the resulting polymer while maintaining the high activity of the catalyst, the effect of controlling the composition distribution of the resulting copolymer, the particle shape of the catalyst particles, It is known to show an aggregating agent effect for controlling the particle size.
- cyclic ester compounds (a) and (b) described above also show an effect of controlling the molecular weight distribution by themselves being electron donors.
- the halogen / titanium (atomic ratio) (that is, the number of moles of halogen atoms / number of moles of titanium atoms) is 2 to 100, preferably 4 to 90.
- Cyclic ester compound (a) / titanium (molar ratio) that is, number of moles of cyclic ester compound (a) / number of moles of titanium atom) and cyclic ester compound (b) / titanium (molar ratio) (that is, cyclic ester compound)
- the number of moles of (b) / number of moles of titanium atoms) is 0.01 to 100, preferably 0.2 to 10.
- the catalyst component (c) has a catalyst component (c) / titanium atom (molar ratio) of 0 to 100, preferably 0 to 10.
- the value (moles) of 100 ⁇ cyclic ester compound (a) / (cyclic ester compound (a) + cyclic ester compound (b)) %) Is 5 mol%, preferably 25 mol%, more preferably 40 mol%, and particularly preferably 50 mol%.
- the upper limit is 99 mol%, preferably 90 mol%, more preferably 85 mol%, particularly preferably 80 mol%.
- the magnesium / titanium (atomic ratio) (that is, the number of moles of magnesium atoms / the number of moles of titanium atoms) is desirably 2 to 100, preferably 4 to 50.
- the content of components other than the cyclic ester compounds (a) and (b) described above, for example, the catalyst component (c) and the catalyst component (d) is preferably cyclic ester compounds (a) and ( b) It is 20 weight% or less with respect to 100 weight%, More preferably, it is 10 weight% or less.
- organometallic compound catalyst component (II) examples include organometallic compounds containing a metal atom selected from Group 1, Group 2 and Group 13 of the periodic table. Specifically, a compound containing a Group 13 metal, such as an organoaluminum compound, a complex alkylated product of a Group 1 metal and aluminum, an organometallic compound of a Group 2 metal, or the like can be used. Among these, an organoaluminum compound is preferable.
- organometallic compound catalyst component (II) examples include organometallic compound catalyst components described in known documents such as EP585869A1.
- the catalyst for olefin polymerization of the present invention may contain an electron donor (III) as necessary together with the organometallic compound catalyst component (II).
- the electron donor (III) is preferably an organosilicon compound.
- this organosilicon compound for example, a compound represented by the following general formula (4) can be exemplified.
- R n Si (OR ′) 4-n (4) (In the formula, R and R ′ are hydrocarbon groups, and n is an integer of 0 ⁇ n ⁇ 4.)
- Specific examples of the organosilicon compound represented by the general formula (4) are diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, Dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methyl Cyclopentyltrimethoxysilane
- vinyltriethoxysilane diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, and dicyclopentyldimethoxysilane are preferably used.
- silane compound represented by the following formula (5) described in International Publication No. 2004/016662 pamphlet is also a preferable example of the organosilicon compound.
- R a is a hydrocarbon group having 1 to 6 carbon atoms, preferably an unsaturated or saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably. Examples thereof include saturated aliphatic hydrocarbon groups having 2 to 6 carbon atoms.
- ethyl group examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n- A hexyl group, a cyclohexyl group, etc. are mentioned, Among these, an ethyl group is particularly preferable.
- R b is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, preferably an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom.
- R b is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, preferably an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom.
- Specific examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, an n-pentyl group, an iso-pentyl group, and a cyclopentyl group.
- R c is a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, preferably an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms.
- Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n- A hexyl group, a cyclohexyl group, an octyl group, etc. are mentioned, Among these, an ethyl group is particularly preferable.
- organosilicon compound is a compound represented by the following formula (6).
- RNSi (OR a ) 3 (6)
- RN represents a cyclic amino group.
- the cyclic amino group include a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, Examples include 2,3,4-tetrahydroisoquinolino group and octamethyleneimino group.
- Examples of Ra include the same as defined in Formula (5).
- organosilicon compounds can be used in combination of two or more.
- Other useful compounds as the electron donor (III) include the aromatic carboxylic acid ester defined as the catalyst component (d) and / or two or more ether bonds via a plurality of carbon atoms.
- a compound (polyether compound) is also a preferred example.
- the olefin polymerization catalyst of the present invention may contain other components useful for olefin polymerization as required in addition to the above components.
- other components include a carrier such as silica, an antistatic agent, a particle flocculant, and a storage stabilizer.
- a particle aggregating agent for example, sorbitan distearate is used as a preferred compound when particles are produced using magnesium chloride and ethanol.
- the production method of the propylene-based block copolymer according to the present invention is not limited as long as the requirements [1] to [3] and preferably the requirements [4] and / or [5] are satisfied.
- the main polymerization is carried out in the presence of a prepolymerization catalyst obtained by prepolymerization of an olefin in the presence of the above-mentioned olefin polymerization catalyst. It is also possible.
- This prepolymerization is carried out by prepolymerizing the olefin in an amount of 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g, per 1 g of the olefin polymerization catalyst.
- a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used.
- the concentration of the solid titanium catalyst component (I) in the prepolymerization is usually about 0.001 to 200 mmol, preferably about 0.01 to 50 mmol, particularly preferably 0, in terms of titanium atom per liter of the liquid medium. Desirably, it is in the range of 1 to 20 mmol.
- the amount of the organometallic compound catalyst component (II) in the prepolymerization may be such that 0.1 to 1000 g, preferably 0.3 to 500 g of polymer is formed per 1 g of the solid titanium catalyst component (I).
- the amount is usually about 0.1 to 300 moles, preferably about 0.5 to 100 moles, particularly preferably 1 to 50 moles per mole of titanium atoms in the solid titanium catalyst component (I). Is desirable.
- the electron donor (III) or the like can be used as necessary.
- these components are added in an amount of 0.1 to 1 per mole of titanium atoms in the solid titanium catalyst component (I). It is used in an amount of 50 mol, preferably 0.5 to 30 mol, more preferably 1 to 10 mol.
- the prepolymerization can be performed under mild conditions by adding an olefin and the above catalyst components to an inert hydrocarbon medium.
- Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene; Cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, cycloheptane, methylcycloheptane, cyclooctane; Aromatic hydrocarbons such as benzene, toluene, xylene; Halogenated hydrocarbons such as ethylene chloride and chlorobenzene; Alternatively, a mixture thereof can be used.
- Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene
- Cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane,
- inert hydrocarbon media it is particularly preferable to use aliphatic hydrocarbons.
- prepolymerization can be carried out using the olefin itself as a solvent, or the prepolymerization can be carried out in a substantially solvent-free state. In this case, it is preferable to perform preliminary polymerization continuously.
- the olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described later, but is preferably propylene.
- the temperature during the prepolymerization is usually ⁇ 20 to + 100 ° C., preferably ⁇ 20 to + 80 ° C., more preferably 0 to + 40 ° C.
- the main polymerization is divided into a process for producing a crystalline propylene-based (co) polymer and a process for producing a copolymer rubber, and is used in any of these processes (that is, polymerized).
- the olefin includes at least one olefin selected from propylene, ethylene and an ⁇ -olefin having 4 to 20 carbon atoms. Specific examples of the ⁇ -olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene.
- Linear olefins such as 1-eicosene, and branched olefins such as 4-methyl-1-pentene, 3-methyl-1-pentene, and 3-methyl-1-butene.
- 1-butene, 1-pentene and 4-methyl-1-pentene are preferred.
- preferred olefin combinations include propylene / ethylene, propylene / 1-butene, propylene / 1-pentene, propylene / 4-methyl-1-pentene, propylene / ethylene / 1-butene, propylene / ethylene / 1- Examples include pentene and propylene / ethylene / 4-methyl-1-pentene.
- those containing 1-butene and 4-methyl-1-pentene as a copolymer are particularly preferable.
- aromatic vinyl compounds such as styrene and allylbenzene; alicyclic vinyl compounds such as vinylcyclohexane and vinylcycloheptane can also be used.
- cyclic olefins such as cyclopentene, cycloheptene, norbornene and tetracyclododecene; conjugated dienes such as isoprene and butadiene; compounds having a polyunsaturated bond such as non-conjugated dienes can also be used as a polymerization raw material.
- These compounds may be used alone or in combination of two or more (hereinafter, the olefin used together with the ethylene and the ⁇ -olefin having 4 to 20 carbon atoms is referred to as “other olefin”. Say).
- aromatic vinyl compounds are preferable.
- other olefins may be used in combination as long as the amount is 100% by weight or less, for example, 10% by weight or less, preferably 5% by weight or less.
- the prepolymerization and the main polymerization can be performed by any of a liquid phase polymerization method such as a bulk polymerization method, a solution polymerization and a suspension polymerization, or a gas phase polymerization method.
- a liquid phase polymerization method such as a bulk polymerization method, a solution polymerization and a suspension polymerization, or a gas phase polymerization method.
- the reaction solvent may be an inert hydrocarbon used during the above-described prepolymerization, or an olefin that is liquid at the reaction temperature and pressure.
- the solid titanium catalyst component (I) is usually about 0.0001 to 0.5 in terms of titanium atoms per liter of polymerization volume. Used in an amount of mmol, preferably about 0.005 to 0.1 mmol.
- the organometallic compound catalyst component (II) is usually used in an amount of about 1 to 2000 mol, preferably about 5 to 500 mol, per 1 mol of titanium atom in the prepolymerization catalyst component in the polymerization system. Used.
- the electron donor (III) is 0.001 to 50 mol, preferably 0.01 to 30 mol, particularly preferably, relative to 1 mol of the organometallic compound catalyst component (II). Is used in an amount of 0.05 to 20 mol.
- the molecular weight of the resulting polymer can be adjusted (lowered), and a polymer having a high melt flow rate can be obtained.
- the polymerization temperature of the olefin is usually about 20 to 200 ° C., preferably about 30 to 100 ° C., more preferably 50 to 90 ° C.
- the pressure is usually set to normal pressure to 100 kgf / cm 2 (9.8 MPa), preferably about 2 to 50 kgf / cm 2 (0.20 to 4.9 MPa).
- the polymerization can be carried out by any of batch, semi-continuous and continuous methods.
- the polymerization can be carried out in two or more stages by changing the reaction conditions. By performing such multistage polymerization, it is possible to further widen the molecular weight distribution of the olefin polymer.
- the n-decane insoluble part (Dinsol) constituting the propylene-based block copolymer of the present invention is a propylene homopolymer, a propylene random polymer (ethylene and a carbon atom having 4 or more carbon atoms). a propylene-based polymer containing a skeleton derived from one or more olefins selected from ⁇ -olefins in an amount not exceeding 1.5 mol%), or a mixture of two or more of these.
- the n-decane soluble part is substantially composed of propylene / ethylene copolymer, propylene / ⁇ -olefin copolymer, propylene / ethylene / ⁇ -olefin copolymer or a mixture of two or more of these.
- the “copolymer” includes a random polymer).
- the propylene block copolymer of the present invention can be produced by any one of the following production methods.
- Method A Propylene system satisfying requirements [1] to [3] and preferably requirements [4] and / or [5] by continuously performing the following two polymerization steps (polymerization step 1 and polymerization step 2) Method for producing a block copolymer (hereinafter, this method is referred to as “straight weight method”, and the propylene-based block copolymer obtained by this method may be referred to as a propylene-based block copolymer (A)). .
- Polymerization step 1 A step of producing a (co) polymer of propylene and, if necessary, one or more olefins selected from ethylene and an ⁇ -olefin having 4 to 20 carbon atoms in the presence of a solid titanium catalyst component (Crystalline propylene (co) polymer production process).
- Polymerization step 2 A step of producing a copolymer of propylene and one or more olefins selected from ethylene and an ⁇ -olefin having 4 to 20 carbon atoms in the presence of a solid titanium catalyst component (copolymer rubber production) Process).
- Method B After the (co) polymer produced in the polymerization step 1 of the method A and the copolymer produced in the polymerization step 2 of the method A are individually produced in the presence of a solid titanium catalyst component, they are physically treated.
- this method “blending method” the propylene-based block copolymer obtained by this method may be referred to as a propylene-based copolymer (B)).
- the propylene-based block copolymer according to the present invention is obtained by homopolymerizing propylene in a propylene medium in the polymerization step 1 in the presence of the above-mentioned olefin polymerization catalyst, as described in Method A, or ethylene and carbon atoms having 4 to 4 carbon atoms.
- Propylene-based copolymer containing a skeleton derived from one or more olefins selected from 20 ⁇ -olefins in an amount not exceeding 1.5 mol% is produced.
- propylene, ethylene, and the number of carbon atoms are Copolymerization with one or more olefins selected from 4 to 20 ⁇ -olefins, and the finally obtained propylene block copolymer is soluble in room temperature n-decane (Dsol) 5 to 80 It is characterized by comprising 20% to 95% by weight and a portion insoluble in room temperature n-decane (Dinsol).
- the decane-insoluble component content is not less than 70% by weight, preferably not less than 85% by weight, particularly preferably not less than 90% by weight.
- a propylene-based block copolymer having a high content, that is, a high content of the crystalline component is obtained.
- the molecular weight distribution can be reduced by the action of the catalyst for olefin polymerization of the present invention without performing multi-stage polymerization, for example, polymerization with a small number of stages, for example, single-stage polymerization.
- a wide propylene polymer can be obtained.
- GPC gel permeation chromatography
- Polypropylene obtained by using a conventional solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor is an index of molecular weight distribution obtained by GPC measurement, for example, in a region where MFR is 1 to 10 g / 10 min.
- MFR is 1 to 10 g / 10 min.
- Mw / Mn value was 6 or less, and the Mz / Mw value was less than 4.
- Mw under the same polymerization conditions as described above.
- the method for producing a propylene-based block copolymer of the present invention it has been found that a polymer having a high Mz / Mw value can be obtained, and the Mz / Mw value is 6.0 to 20, preferably It is 6.5 to 18, more preferably 7 to 15.
- the upper limit of the Mz / Mn value is preferably 300, more preferably 250, and particularly preferably 200.
- the lower limit is preferably 70, more preferably 100, and particularly preferably 120.
- a polymer having a high Mz / Mw value and Mz / Mn value is often obtained.
- a propylene polymer having a high Mw / Mn value is excellent in moldability and rigidity.
- a high Mz / Mw value indicates a high content ratio of components having a high molecular weight, and it is easily predicted that the resulting propylene polymer has a high melt tension and a high possibility of excellent moldability. Is done.
- a polymer having a wide molecular weight distribution that is, a high Mw / Mn value can be obtained without performing multi-stage polymerization.
- a propylene polymer excellent in moldability and rigidity can be obtained in a simple form.
- a polymer having a wider molecular weight distribution can be produced, and the polymer is excellent in melt tension and moldability. It is expected that.
- a method for producing a propylene-based block copolymer if a method for producing a propylene-based block copolymer is used, a polymer having a high content of high molecular weight components, that is, a polymer having a high Mz / Mw value and Mz / Mn value can be obtained. This makes it possible to reduce the number of injection molding and injection molding cycles for large products, improve the appearance of injection molded products, and improve blow moldability and foam moldability. It becomes possible to impart molding processability.
- the polymer obtained by these methods is relatively complicated. May not be sufficiently improved in melt tension and moldability. This is presumed that polymers having different molecular weights are basically difficult to mix.
- the polymer obtained by the method for producing a propylene-based block copolymer of the present invention has a high melt tension because a polymer having different molecular weights in a very wide range is mixed at the catalyst level, that is, at the nano level. It is expected that the moldability is excellent.
- the propylene block copolymer of the present invention is characterized in that there are few metal residues derived from the catalyst because it uses a highly active catalyst.
- a propylene polymer obtained by using a titanium trichloride catalyst well known as a catalyst capable of wide molecular weight distribution has many metal residues in the polymer because of its low activity. Although it varies depending on the application, it is said that when there are many metal residues, it often causes adverse effects such as deterioration in appearance and resin physical properties or coloration of the resin. For this reason, in general, deashing treatment is performed by applying heat using alcohol, acid, or the like to remove the metal component derived from the catalyst remaining in the polymer. In the case of a titanium trichloride-based catalyst, the titanium metal contained in the polymer before deashing is about 30 to 200 ppm, but it can be lowered to 2 to 50 ppm by deashing treatment.
- the titanium metal component before deashing is 1 to 30 ppm in the polymer, and 0.1 to It can be reduced to 2 ppm.
- the propylene resin composition according to the present invention is a mixture of the propylene-based block copolymer according to the present invention, various additives shown below, and preferably an inorganic filler and / or an elastomer.
- ⁇ Stabilizer contained in propylene resin composition As the stabilizer used in the present invention, known stabilizers such as a heat stabilizer, a weather stabilizer, a light stabilizer, a chloride absorbent, a filler, a crystal nucleating agent, and a softening agent can be used without limitation.
- known stabilizers such as a heat stabilizer, a weather stabilizer, a light stabilizer, a chloride absorbent, a filler, a crystal nucleating agent, and a softening agent can be used without limitation.
- known phenol stabilizers, organic phosphite stabilizers, thioether stabilizers, hindered amine stabilizers, higher fatty acid metal salts such as calcium stearate, inorganic oxides, and glass fibers for example, known phenol stabilizers, organic phosphite stabilizers, thioether stabilizers, hindered amine stabilizers, higher fatty acid metal salts such as calcium stearate,
- the polypropylene resin composition according to the present invention further includes other heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, Wax etc. may be included.
- the propylene resin composition according to the present invention may contain an elastomer component for the purpose of imparting impact resistance.
- an elastomer a propylene / ⁇ -olefin block copolymer, an ethylene / ⁇ -olefin random copolymer, an ethylene / ⁇ -olefin / non-conjugated polyene random copolymer different from the propylene block copolymer of the present invention are used.
- These elastomer components are not particularly limited, but are preferably 1 to 100 parts by weight, more preferably 3 to 60 parts by weight with respect to 100 parts by weight of the propylene-based block copolymer of the present invention.
- propylene polymer components may be added to the propylene-based resin composition according to the present invention as long as the effects of the invention are not impaired.
- the propylene resin composition according to the present invention is within the range not impairing the object of the present invention, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, Basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, guffite, aluminum powder Inorganic fillers such as molybdenum sulfide, boron fiber, and silicon carbide fiber, and organic fillers such as polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber, and carbon fiber may be included. These fillers are not particularly limited, but are preferably 1 to 100 parts by weight, more preferably 3 to 60 parts by weight, based on 100 parts by weight of the propylene-based block copolymer of
- the propylene-based block copolymer used in the present invention is characterized by containing a relatively large amount of high molecular weight components as described above. It is known that high molecular weight components tend to be relatively easily cut by energy such as heat, light, and shear. When molecular cutting occurs, the molecular weight distribution becomes narrow, which may cause problems such as a reduction in high-speed molding performance and difficulty in manufacturing a large molded product. Therefore, it is preferable to select an additive having a higher effect than the conventional additive and increase the amount of the additive.
- Examples of the resin molded body made of the propylene-based block copolymer include an injection molded body, a foam molded body, an injection foam molded body, an extrusion molded body, a blow molded body, a vacuum / pressure molded body, a calendar molded body, a stretched film, and an inflation film. A film etc. are mentioned.
- the injection-molded article according to the present invention has a good balance between rigidity and low-temperature impact resistance, and has a good appearance of the molded article, such as no defects such as flow marks and bumps. Therefore, the use of the injection-molded product according to the present invention is not limited, but in particular, automotive exterior parts such as bumpers, side moldings, fenders, and under covers, automotive interior parts such as instrument panels, door trims, pillars, and engines. It can be suitably used for room peripheral parts, other automobile parts, home appliance parts, food containers, beverage containers, medical containers, containers and the like.
- molding conditions for the injection-molded article of the present invention conventionally known conditions can be adopted without limitation.
- the foam molded article of the present invention is obtained by heating a foam molding resin composition comprising the propylene-based block copolymer of the present invention, a foaming agent, and if necessary, an organic peroxide and a crosslinking aid. Can be manufactured.
- the following two methods can be mainly exemplified as a general method for producing a foam molded article.
- the decomposable foaming agent used in the method (1) is a compound that decomposes the foaming agent to generate a gas such as carbon dioxide gas or nitrogen gas, and is an organic foaming agent even if it is an inorganic foaming agent. Alternatively, an organic acid that promotes gas generation may be added in combination. Specific examples of the decomposable foaming agent include the following compounds.
- Inorganic foaming agent sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, citric acid, sodium citrate and the like.
- N-nitroso compounds such as N, N′-dinitrosoterephthalamide, N, N′-dinitrosopentamethylenetetramine
- azodicarbonamide azobisisobutyronitrile
- azocyclohexylnitrile Azo compounds such as azodiaminobenzene and barium azodicarboxylate
- azide compounds such as calcium azide, 4,4′-diphenyldisulfonyl azide, p-toluenesulfonyl azide, and the like.
- foaming agents can be used singly or in combination of two or more. Of these, carbonates or bicarbonates such as sodium bicarbonate are preferred.
- the addition amount (kneading amount) of the foaming agent may be selected according to the type of foaming agent and the target foaming ratio, but is within the range of 0.5 to 100 parts by weight with respect to 100 parts by weight of the propylene-based block copolymer. It is preferable that it exists in.
- an organic carboxylic acid such as citric acid or a foaming nucleating agent such as talc may be used in combination.
- the foam nucleating agent is preferably used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the propylene-based block copolymer.
- both the propylene-based block copolymer and the decomposable foaming agent are supplied to a melt extruder, and gas is generated by thermally decomposing the foaming agent while melt kneading at an appropriate temperature.
- a foam can be molded by discharging the molten propylene-based block copolymer containing gas from a die.
- the melt kneading temperature and the melt kneading time in this method may be appropriately selected depending on the foaming agent used and the kneading conditions. Usually, the melt kneading temperature is 170 to 300 ° C. and the melt kneading time can be 1 to 60 minutes.
- Preferred examples of the volatile foaming agent used in the method (2) include aliphatic hydrocarbons such as propane, butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclobutane, cyclopentane and cyclohexane.
- the addition amount (kneading amount) of the foaming agent in the method (2) varies depending on the type of foaming agent and the target foaming ratio, but is 0.5 to 100 parts by weight with respect to 100 parts by weight of the propylene-based block copolymer. It is preferable to be within the range.
- the propylene-based block copolymer is melted in an extruder, the volatile foaming agent is pressed into the extruder, and the molten propylene-based block copolymer is maintained at a high pressure.
- the foam can be molded by extruding a kneaded body of the sufficiently kneaded propylene block copolymer and the volatile foaming agent from a die.
- the melt kneading temperature and melt kneading time in this method may be appropriately selected depending on the foaming agent used and the kneading conditions, and the melt kneading temperature is usually 130 to 300 ° C. and the melt kneading time is usually 1 to 120 minutes. .
- an organic peroxide may be used as necessary.
- This organic peroxide is preferably used in an amount of 0.01 to 5 parts by weight, particularly 0.01 to 1 part by weight, based on 100 parts by weight of the propylene-based block copolymer.
- a crosslinking aid may be used as necessary.
- the crosslinking aid stabilizes the polymer radical by simultaneously removing the hydrogen of the olefin polymer by the organic peroxide and causing the resulting polymer radical to react with the crosslinking aid faster than causing the cleavage reaction. It works to increase the crosslinking efficiency.
- the crosslinking aid having such a function include unsaturated compounds having one or more double bonds, oxime compounds, nitroso compounds, maleimide compounds and the like. These are used in one kind or a mixture of two or more kinds.
- the shape of the foamed molded product according to the present invention may be any shape, and may be a block shape, a sheet shape, or a monofilament shape.
- a conventionally known foam molding apparatus can be used.
- conventionally known conditions can be adopted as the molding conditions.
- the propylene-based block copolymer if necessary, an organic peroxide, a crosslinking aid, a foaming agent and, if necessary, a heat-resistant stabilizer, a Henschel mixer, a V-blender, a ribbon blender,
- the composition mixed in a tumbler blender or the like is kneaded using an extruder, preferably an extruder with a vent, while absorbing unnecessary volatile substances from a vent installed after the high-temperature heating section.
- the organic peroxide is blended, the organic peroxide is kneaded in a temperature range that decomposes but does not decompose the foaming agent.
- It can be formed into a foam by discharging a melt having foam cells from a T die or a cylindrical die and preferably forming a sheet.
- the cylindrical sheet When discharged from a cylindrical die, the cylindrical sheet is usually cut into one or more and then the smoothed sheet is taken up.
- the foam molded body produced from the propylene-based block copolymer obtained by the method of the present invention is suitable for lightness, heat insulation, buffering of external stress or compressive strength, so that its density is It is preferably in the range of 0.09 to 0.6 g / cm 3 , particularly preferably in the range of 0.15 to 0.3 g / cm 3 . Accordingly, the expansion ratio of the foamed molded product is preferably 1.3 to 10 times, particularly 1.6 to 6 times.
- the product application of the foamed molded product according to the present invention is not particularly limited, and specifically, stationery supplies such as file cases, automotive interior materials such as automotive roof liners, trays, food trays, noodle containers, lunch boxes, Fast food containers, retort containers, frozen food containers, sugar beet containers, microwave oven heat resistant containers, cups, synthetic wood, various foam materials, various cushioning materials, various heat insulating materials, various soundproofing materials, various vibration-proofing materials, etc. It is done.
- stationery supplies such as file cases, automotive interior materials such as automotive roof liners, trays, food trays, noodle containers, lunch boxes, Fast food containers, retort containers, frozen food containers, sugar beet containers, microwave oven heat resistant containers, cups, synthetic wood, various foam materials, various cushioning materials, various heat insulating materials, various soundproofing materials, various vibration-proofing materials, etc. It is done.
- the propylene-based block copolymer of the present invention has a high melt tension and an excellent balance between rigidity and impact resistance. Therefore, the propylene-based block copolymer of the present invention has a higher foaming ratio and a good surface appearance than the propylene-based block copolymer of the present invention. An injection foam molded article having excellent mechanical strength can be obtained.
- An injection foam molded article according to the present invention is obtained by injecting a resin composition for an injection foam molded article comprising the propylene-based block copolymer, a foaming agent, and if necessary, an organic peroxide, a crosslinking aid and the like. It can be manufactured by foam molding.
- the propylene-based block copolymer is injected in the form of a propylene-based resin composition in which an inorganic filler and / or an organic filler and an elastomer component are added. Foam molding may be performed.
- the foaming agent that can be used for injection foaming is not particularly limited as long as it can be normally used for injection foaming, such as a chemical foaming agent and a physical foaming agent.
- the chemical foaming agent is mixed with the resin in advance and then supplied to the injection molding machine, and decomposes in the cylinder to generate a gas such as carbon dioxide.
- Examples of the chemical foaming agent include inorganic chemical foaming agents such as sodium bicarbonate and ammonium carbonate, and organic chemical foaming agents such as azodicarbonamide and N, N′-dinitrosopentamethylenetetramine.
- a physical foaming agent is injected into a molten resin in a cylinder of a molding machine as a gaseous or supercritical fluid, dispersed or dissolved, and functions as a foaming agent by being released from pressure after being injected into a mold. Is.
- Physical foaming agents include aliphatic hydrocarbons such as propane and butane, alicyclic hydrocarbons such as cyclobutane and cyclopentane, halogenated hydrocarbons such as chlorodifluoromethane and dichloromethane, nitrogen, carbon dioxide, air, etc. Inorganic gas. You may use these individually or in mixture of 2 or more types.
- Chemical foaming agents are inorganic chemical foaming agents, physical foaming agents are nitrogen and carbon dioxide. Inorganic gas such as air is preferable.
- foaming agents include, for example, foaming aids such as organic acids such as citric acid and inorganic fine particles such as talc and lithium carbonate, in order to stably and uniformly make the foamed foam air bubbles.
- foaming aids such as organic acids such as citric acid and inorganic fine particles such as talc and lithium carbonate, in order to stably and uniformly make the foamed foam air bubbles.
- a nucleating agent such as may be added.
- the inorganic chemical foaming agent is preferably used as a masterbatch of a polyolefin resin having a concentration of 10 to 50% by weight from the viewpoints of handleability, storage stability, and dispersibility in a polypropylene resin.
- the amount of the foaming agent used may be set as appropriate depending on the foaming ratio of the final product, the type of foaming agent, and the resin temperature during molding.
- an inorganic chemical foaming agent in 100 parts by weight of the propylene block copolymer of the present invention, preferably 0.5 parts by weight or more and 20 parts by weight or less, more preferably 1 part by weight or more and 10 parts by weight. It is used within the range of parts. By using in this range, it is easy to economically obtain a foamed molded article having a foaming ratio of 2 times or more and uniform fine cells.
- antioxidants such as antioxidants, metal deactivators, phosphorus processing stabilizers, UV absorbers, UV stabilizers, fluorescent brighteners, metal soaps, antacid adsorption
- An additive such as a stabilizer such as an agent, a crosslinking agent, a chain transfer agent, a nucleating agent, a plasticizer, a filler, a reinforcing material, a pigment, a dye, a flame retardant, and an antistatic agent may be used in combination.
- additives used as necessary are used in a range that does not impair the effects of the present invention, but preferably 0 with respect to 100 parts by weight of the propylene-based block copolymer of the present invention. 0.01 parts by weight or more and 10 parts by weight or less is used.
- the injection foam molding method itself, a known method can be applied, and the molding conditions may be appropriately adjusted depending on the MFR of the polypropylene resin, the type of foaming agent, the type of molding machine, or the shape of the mold.
- the resin temperature is 170 to 250 ° C.
- the mold temperature is 10 to 100 ° C.
- the molding cycle is 1 to 60 minutes
- the injection speed is 10 to 300 mm / second
- the injection pressure is 10 to 200 MPa.
- foaming in the mold There are various methods for foaming in the mold. Among them, a mold composed of a fixed mold and a movable mold capable of moving forward and backward at an arbitrary position is used.
- the so-called core back method (Moving Cavity method), which is caused to recede and foam, forms a non-foamed layer on the surface, the foamed layer tends to become uniform fine cells, and a foamed article with excellent lightness can be easily obtained.
- This is preferable.
- As a method for retracting the movable mold it may be performed in one step, may be performed in multiple steps of two or more steps, and the speed of retraction may be adjusted as appropriate. In this way, an injection foam molded article can be obtained.
- the propylene-based block copolymer according to the present invention has high fluidity at the time of melting and high melt tension.
- a large injection-foamed molded article having a good appearance can be obtained.
- the injection-foamed molded article can be widely used for automobile interior materials such as luggage boxes, console boxes, tool boxes, door trims, food packaging containers, home appliance housings, daily miscellaneous goods boxes, and the like.
- the extruded product according to the present invention is produced by molding by the extrusion method using the propylene-based block copolymer of the present invention. Since the propylene-based block copolymer has a high melt tension, it can be molded at a high speed during extrusion molding, or a large product can be obtained.
- a conventionally known extrusion device can be used.
- a single screw extruder, a kneading extruder, a ram extruder, a gear extruder, or the like is used.
- An annular die or a T die may be attached to the extruder.
- molding conditions Conventionly known conditions can be adopted as the molding conditions.
- a sheet is molded at a resin temperature of 100 to 300 ° C., preferably 150 to 270 ° C., and at a T die temperature of 80 ° C. to 270 ° C., preferably 130 ° C. to 250 ° C. Is mentioned.
- the extrudates include so-called deformed extrudates having surface features such as wood grain.
- the profile extrusion-molded product according to the present invention is produced by molding by the profile extrusion method using the propylene-based block copolymer. Since the propylene-based block copolymer has a high melt tension, there is a tendency that the shapeability is excellent and the drawdown property is improved.
- the profile extrusion molded body is a resin containing a filler separately from a method of feeding a resin containing a filler such as wood powder and talc to an extruder and extruding from a die having a desired shape, and a base resin.
- Conventionally known methods such as a method of side-feeding to the extruder can be employed. Specifically, a method described in JP 2002-138176 A can be employed.
- the product application of the extruded product according to the present invention is not particularly limited, but specifically, it is a modified press such as a gutter, a curtain rail, a window frame, a shelf, a door, other building materials, a wiring duct, a roller den shutter, and a shutter.
- a modified press such as a gutter, a curtain rail, a window frame, a shelf, a door, other building materials, a wiring duct, a roller den shutter, and a shutter.
- Others include tubes, pipes, hoses, electric wires (coating), films, sheets, plates, fibers, tapes, monofilaments, etc.
- the blow molded product according to the present invention is produced by molding by the blow method using the propylene-based block copolymer of the present invention. Since the propylene-based block copolymer has a high melt tension, it can be molded at a high speed during blow molding, or a large product can be obtained.
- blow molding apparatus In order to produce the blow molded article according to the present invention from the propylene-based block copolymer, a conventionally known blow molding apparatus can be used. Also, conventionally known conditions can be adopted as the molding conditions. In this invention, it is preferable to manufacture a molded object on the following conditions among such molding conditions.
- a parison on a tube is formed from a die at a resin temperature of 170 to 300 ° C., preferably 170 to 270 ° C., and then air is blown after holding the parison into a corresponding mold.
- the draw ratio at this time can be preferably set to about 1.5 to 10 times in the transverse direction.
- the product application of the blow molded article according to the present invention is not particularly limited.
- automotive exterior materials such as automobile bumpers, automobile spoilers, side moldings, front grill guards, and bumper guards; sun visors and radiator tanks
- Automotive interior materials such as washer tanks, ducts, distributors, evaporator cases, console boxes, indicator panels, door trims; kerosene tanks, food containers, shampoo containers, cosmetic containers, detergent containers, chemical containers, toner containers, etc. Containers; other toys and containers.
- the vacuum / pressure molded body according to the present invention is produced by molding a sheet comprising the propylene-based block copolymer of the present invention by a vacuum molding method or a pressure molding method. Since the propylene-based block copolymer has a high melt tension, the sheet is sufficiently deformed along the mold shape. Therefore, the vacuum / compressed air molded body according to the present invention can be enlarged in size and can be deep drawn.
- a conventionally known vacuum molding apparatus or pressure molding apparatus can be used. Also, conventionally known conditions can be adopted as the molding conditions.
- the sheet-like molded product of the propylene-based block copolymer is held on a mold having a shape to be applied at a temperature of 180 ° C. to 300 ° C., preferably 100 ° C. to 270 ° C., particularly preferably 120 ° C. to 250 ° C.
- a mold having a shape to be applied at a temperature of 180 ° C. to 300 ° C. preferably 100 ° C. to 270 ° C., particularly preferably 120 ° C. to 250 ° C.
- Examples of the method for obtaining a vacuum and a compressed air molded body by evacuating the inside of the mold, injecting a compressed gas into the mold, or injecting a compressed gas into the mold can be exemplified.
- the product application of the vacuum / compressed air product according to the present invention is not particularly limited, and specifically, automotive interior materials such as automobile roof liners, refrigerator interior materials, washing machine interior and exterior materials, jelly containers, disposable lunch boxes, trays Food trays, food foaming trays, tofu packs, cups, bags, microwave heat resistant containers, machine protective cases, product packaging cases, and the like.
- automotive interior materials such as automobile roof liners, refrigerator interior materials, washing machine interior and exterior materials, jelly containers, disposable lunch boxes, trays Food trays, food foaming trays, tofu packs, cups, bags, microwave heat resistant containers, machine protective cases, product packaging cases, and the like.
- the calendered molding according to the present invention is produced by molding by the calendering method using the propylene-based block copolymer of the present invention. Since the propylene-based block copolymer has a high melt tension, a film with little thickness unevenness can be obtained.
- a conventionally known calender apparatus can be used for producing the calender molded body according to the present invention from the propylene-based block copolymer. Also, conventionally known conditions can be adopted as the molding conditions.
- examples of the molding apparatus include an in-line type, an L type, an inverted L type, and a Z type.
- the resin temperature is 100 ° C to 300 ° C, preferably 130 ° C to 270 ° C
- the roll temperature is 100 ° C to 350 ° C, preferably 130 ° C to 300 ° C, particularly preferably 150 ° C to 270 ° C. .
- paper and cloth can be sent to the roll to make artificial leather, waterproof cloth and various laminate products.
- the product application of the calendered product according to the present invention is not particularly limited, and specific examples include various card stocks and daily goods.
- the stretched film which concerns on this invention is manufactured by shape
- the stretched film according to the present invention has a thickness of usually 5 to 200 ⁇ m, preferably 10 to 120 ⁇ m.
- the stretched film according to the present invention is usually 20 to 70 times, preferably 40 to 60 times in the case of a biaxially stretched film, and usually 2 to 10 times, preferably 2 to 6 times in the case of a uniaxially stretched film. It is.
- a conventionally known stretching apparatus can be used.
- a tender method longitudinal and transverse stretching, transverse and longitudinal stretching
- simultaneous biaxial stretching method simultaneous biaxial stretching method
- uniaxial stretching method uniaxial stretching method
- molding conditions can be adopted as the molding conditions.
- a method of producing a stretched film by melt-extrusion at 220 to 280 ° C., preferably 240 to 270 ° C., and stretching 2 to 10 times, preferably 2 to 6 times in the machine direction can be exemplified.
- the product use of the stretched film according to the present invention is not particularly limited, specifically, food packaging films such as confectionery and vegetable packaging; shrink films such as cup noodles; fiber packaging such as shirts, T-shirts and pantyhose Films for stationery such as clear files and clear sheets; cigarette packaging films, light packaging films, decorative tapes, packaging tapes and the like.
- the blown film according to the present invention is produced by molding the propylene block copolymer of the present invention by a blown method. Since the propylene-based block copolymer has a high melt tension, bubbles are stable at the time of molding, and the formation speed can be increased at the time of production.
- a conventionally known inflation device In order to produce the inflation film according to the present invention from the propylene-based block copolymer, a conventionally known inflation device can be used. Also, conventionally known conditions can be adopted as the molding conditions.
- a resin temperature of 180 ° C. to 240 ° C., cooling air: 1 stage or 2 stage temperature of 10 ° C. to 40 ° C., take-up speed: 5 m / min to 200 m / min, and expansion ratio: 1.1 times to 5 times are adopted. be able to.
- Such a blown film has a thickness in the range of about 10 ⁇ m to 1 mm, preferably about 15 ⁇ m to 0.5 mm.
- the product use of the inflation film according to the present invention is not particularly limited, specifically, food packaging films such as confectionery and vegetable packaging; fiber packaging films such as shirts, T-shirts and pantyhose; clear files and clears Films for stationery such as sheets; cleaning bags, fashion bag films, agricultural films, cups and the like.
- the molded body made of the propylene-based block copolymer of the present invention can be obtained by using a known molding method such as a stamping mold molding method in addition to the above-mentioned molded products.
- the bulk specific gravity, melt flow rate, intrinsic viscosity ([ ⁇ ]), room temperature n-decane soluble (insoluble) component amount, and molecular weight distribution of the propylene block copolymer were measured by the following methods.
- Melt flow rate (MFR: [g / 10 min]): Based on ASTM D1238E, it was measured with a 2.16 kg load. The measurement temperature was 230 ° C.
- n-decane soluble (insoluble) component amount [wt%]: About 3 g of a propylene-based block copolymer (measured to a unit of 10 -4 g. In addition, this weight was expressed as b (g) in the following formula), 500 ml of decane, and decane. A small amount of a heat-resistant stabilizer was charged, and the mixture was heated to 150 ° C. in 2 hours while stirring with a stirrer in a nitrogen atmosphere to dissolve the propylene-based block copolymer, and kept at 150 ° C. for 2 hours. It was gradually cooled to 23 ° C. over 8 hours.
- the resulting liquid containing the propylene block copolymer precipitate was filtered under reduced pressure through a 25G-4 standard glass filter manufactured by Iwata Glass Co., Ltd. 100 ml of the filtrate was collected and dried under reduced pressure to obtain a part of the decane-soluble component, and this weight was measured to the unit of 10 ⁇ 4 g (this weight is expressed as a (g) in the following equation). did). After this operation, the amount of decane soluble component was determined by the following formula.
- Mobile phase medium o-dichlorobenzene Flow rate: 1.0 ml / min Measurement temperature: 140 ° C.
- Calibration curve creation method Standard polystyrene sample used Sample concentration: 0.10% (w / w) Sample solution volume: 500 ⁇ l Mw / Mn value, Mz / Mw value, and Mz / Mn value were calculated by analyzing the obtained chromatogram by a known method. The measurement time per sample was 60 minutes.
- Pentad fraction (mmmm: [%])
- the microstructure tacticity (mmmm: [%]) were assigned based on Macromolecules 8, 687 (1975) in the propylene polymer 13 It was calculated from the peak intensity ratio of the C-NMR spectrum.
- the 13 C-NMR spectrum was measured using an EX-400 apparatus manufactured by JEOL, based on TMS, at a temperature of 130 ° C., and an o-dichlorobenzene solvent.
- Test piece 12.7 mm (width) x 6.4 mm (thickness) x 127 mm (length) Bending speed: 2.8 mm / min Bending span: 100 mm (JIS small test piece)
- the flexural modulus (FM: [MPa]) was measured according to JIS K7171 under the following conditions.
- Test piece 10 mm (width) x 4 mm (thickness) x 80 mm (length) Bending speed: 2 mm / min Bending span: 64 mm (7) Izod impact strength (ASTM test piece) Izod impact strength (IZ: [J / m]) was measured under the following conditions in accordance with ASTM D256.
- Test piece ASTM-1 dumbbell 19 mm (width) x 3.2 mm (thickness) x 165 mm (length)
- Tensile speed 50 mm / min Distance between spans: 115 mm (JIS small test piece)
- the tensile elongation at break (EL: [%]) was measured according to JIS K7162-BA.
- Test piece JIS K7162-BA dumbbell 5 mm (width) x 2 mm (thickness) x 75 mm (length) Tensile speed: 20 mm / min Distance between spans: 58 mm (10) Heat distortion temperature (ASTM test piece) The heat distortion temperature (HDT: [° C.]) was measured according to ASTM D648.
- Test piece 12.7 mm (width) x 6.4 mm (thickness) x 127 mm (length) Load: 0.45 MPa
- Test piece thickness 1/4 inch (JIS small test piece)
- the heat distortion temperature (HDT: [° C.]) was measured under the following conditions in accordance with JIS K7191.
- Swell Swell was measured according to the following using a capillograph (manufactured by Toyo Seiki Co., Ltd.).
- Measuring apparatus TMA2940 (manufactured by TA Instrument Co., Ltd.) Test temperature range: -40 to 110 ° C Test load: 0.029 N (3 g) (probe: about 3 mm ⁇ ) Temperature increase rate: 5 ° C / min Measurement direction: MD (Machine Direction) direction (flow direction) and TD (Transverse Direction) direction (vertical direction) of the injection molded body Annealing treatment: None Test piece: Square plate (100 mm (width) x 100 mm (length) x 2 mm (thickness)), small square plate (30 mm (width) x 30 mm (length) x 2 mm (thickness)) [Example 1] (Preparation of solid titanium catalyst component ( ⁇ 1)) Anhydrous magnesium chloride (75 g), decane (280.3 g), and 2-ethylhexyl alcohol (308.3 g) were heated and reacted at 130 ° C. for 3 hours to obtain a homogeneous solution. E
- composition of the solid titanium catalyst component ( ⁇ 1) thus obtained was 3.0% by weight of titanium, 18% by weight of magnesium, 58% by weight of chlorine, and diisobutyl 3,6-dimethylcyclohexane 1,2-dicarboxylate. They were 6% by mass, 4.2% by mass of cyclohexane 1,2-dicarboxylate diisobutyl and 0.6% by mass of 2-ethylhexyl alcohol residue.
- Solid titanium catalyst component ( ⁇ 1) prepolymerization A heptane slurry containing 120 g (75.2 mmol-Ti) of the above solid titanium catalyst component ( ⁇ 1) was charged into a three-necked flask equipped with a stirrer with an internal volume of 2 liters substituted with nitrogen, and further dehydrated. Heptane was added to bring the total volume to 1 liter. The mixture was stirred while being controlled at 20 ° C. or lower, and 226 mmol of triethylaluminum was added.
- the obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized.
- propylene was supplied at 30 kg / hr and hydrogen was supplied at 180 NL / hr.
- Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.3 MPa / G.
- the obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 L, and 20 wt% of the polyoxyethylene polyoxypropylene glycol compound was added to the transition metal solid component.
- the slurry was gasified and subjected to gas-solid separation, and then a polypropylene homopolymer powder was sent to a 480 L gas phase polymerization vessel to carry out ethylene / propylene block copolymerization.
- Polymerization was performed at a polymerization temperature of 70 ° C., a pressure of 0.73 MPa / G, and a residence time of 0.63 hours to obtain a propylene-based block copolymer (A-1).
- the room temperature n-decane soluble part (Dsol) was 11.5% by weight, and the room temperature n-decane insoluble part (Dinsol) was 88.5% by weight.
- Cylinder temperature 230 ° C Mold temperature: 40 °C ⁇ Injection molding conditions of square plate for measuring linear expansion coefficient>
- Injection molding machine Part number AUTOSHOTS Series MODEL100D, manufactured by FANUC Cylinder temperature: 230 ° C Mold temperature: 40 °C
- Test piece Square plate (100 mm x 100 mm x 2 mm) [Comparative Example 1] (Preparation of solid titanium catalyst component ( ⁇ 1)) Anhydrous magnesium chloride (75 g), decane (280.3 g), and 2-ethylhexyl alcohol (308.3 g) were heated and reacted at 130 ° C. for 3 hours to obtain a homogeneous solution. Ethyl benzoate (17.7 g) was added to the solution, and the temperature was further increased to 130 ° C. The mixture was stirred for 1 hour.
- the solid part was collected by hot filtration, and the solid part was resuspended in 100 ml of titanium tetrachloride, and then heated again at 110 ° C. for 35 minutes. After completion of the reaction, the solid part was again collected by hot filtration, and thoroughly washed with 100 ° C. decane and hexane until no free titanium compound was detected in the washing solution.
- the solid titanium catalyst component ( ⁇ 1) prepared by the above operation was stored as a decanslurry, but a part of this was dried for the purpose of examining the catalyst composition.
- composition of the solid titanium catalyst component ( ⁇ 1) thus obtained was 2.6% by mass of titanium, 18% by mass of magnesium, 21.2% by mass of diisobutylcyclohexane 1,2-dicarboxylate and 2-ethylhexyl alcohol residue. It was 0.6 mass%.
- Solid titanium catalyst component ( ⁇ 1) prepolymerization A heptane slurry containing 120 g (60.1 mmol-Ti) of the above solid titanium catalyst component ( ⁇ 1) was charged into a three-necked flask equipped with a stirrer with an internal volume of 2 liters substituted with nitrogen, and further dehydrated. Heptane was added to bring the total volume to 1 liter. This was stirred while being controlled to 20 ° C. or less, and 180 mmol of triethylaluminum was added.
- the obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized.
- propylene was supplied at 30 kg / hr and hydrogen was supplied at 170 NL / hr.
- Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.3 MPa / G.
- the obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 L, and 20 wt% of the polyoxyethylene polyoxypropylene glycol compound was added to the transition metal solid component.
- the slurry was gasified and subjected to gas-solid separation, and then a polypropylene homopolymer powder was sent to a 480 L gas phase polymerization vessel to carry out ethylene / propylene block copolymerization.
- Polymerization was carried out at a polymerization temperature of 70 ° C., a pressure of 0.83 MPa / G, and a residence time of 0.51 hours to obtain a propylene-based block copolymer (A′-1).
- the propylene block copolymer (A′-1) was molded in the same manner as in Example 1.
- Table 1 shows the evaluation results of the physical properties of the molded product, the appearance of the injection molded product, and the fluidity of injection molding.
- the solid titanium catalyst component ( ⁇ 2) prepared by the above operation was stored as a decanslurry, but a part of this was dried for the purpose of examining the catalyst composition.
- the composition of the solid titanium catalyst component ( ⁇ 2) thus obtained was 2.4% by mass of titanium, 18% by mass of magnesium, 15.4% by mass of diisobutyl phthalate and 1.2% by mass of 2-ethylhexyl alcohol residue. there were.
- Solid titanium catalyst component ( ⁇ 2) prepolymerization A heptane slurry containing 120 grams (65.1 mmol-Ti) of the above solid titanium catalyst component was charged into a three-neck flask with a stirrer having an internal volume of 2 liters substituted with nitrogen, and dehydrated heptane was further added. The total volume was 1 liter. The mixture was stirred while being controlled at 20 ° C. or lower, and 195 mmol of triethylaluminum was added.
- the obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized.
- propylene was supplied at 30 kg / hr and hydrogen was supplied at 143 NL / hr.
- Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 3.2 MPa / G.
- the obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 L, and 20 wt% of the polyoxyethylene polyoxypropylene glycol compound was added to the transition metal solid component.
- the slurry was gasified and subjected to gas-solid separation, and then a polypropylene homopolymer powder was sent to a 480 L gas phase polymerization vessel to carry out ethylene / propylene block copolymerization.
- Polymerization was performed at a polymerization temperature of 70 ° C., a pressure of 0.96 MPa / G, and a residence time of 0.55 hours to obtain a propylene-based block copolymer (A′-2).
- the propylene block copolymer (A′-2) was molded in the same manner as in Example 1.
- Table 1 shows the evaluation results of the physical properties of the molded product, the appearance of the injection molded product, and the fluidity of injection molding.
- a photograph of the injection molded product used for the flow mark evaluation is shown in FIG.
- Example 2 Polymerization was carried out in the same manner as in Example 1 except that the solid titanium catalyst component ( ⁇ 1) was used and the residence time was 0.47 hours under the polymerization conditions of the gas phase polymerization vessel, and the propylene-based block copolymer (A- 2) was obtained.
- the room temperature n-decane soluble part (Dsol) was 8.6% by weight, and the room temperature n-decane insoluble part (Dinsol) was 91.4% by weight.
- Comparative Example 3 Polymerization was carried out in the same manner as in Comparative Example 1 except that the solid titanium catalyst component ( ⁇ 1) was used and the residence time was 0.37 hours under the polymerization conditions of the gas phase polymerization vessel, and the propylene-based block copolymer (A ′ -3) was obtained.
- Comparative Example 4 Polymerization was carried out in the same manner as in Comparative Example 2 except that the solid titanium catalyst component ( ⁇ 2) was used and the residence time was 0.41 hours under the polymerization conditions of the gas phase polymerization vessel, and the propylene-based block copolymer (A ′ -4) was obtained.
- Example 3 Polymerization was carried out in the same manner as in Example 1 except that the solid titanium catalyst component ( ⁇ 1) was used and the residence time was 0.32 hours under the polymerization conditions of the gas phase polymerization vessel, and the propylene block copolymer (A- 3) was obtained.
- the room temperature n-decane soluble part (Dsol) was 5.9% by weight, and the room temperature n-decane insoluble part (Dinsol) was 94.1% by weight.
- Comparative Example 5 Polymerization was carried out in the same manner as in Comparative Example 1 except that the solid titanium catalyst component ( ⁇ 1) was used and the residence time was 0.26 hours under the polymerization conditions of the gas phase polymerization vessel, and the propylene-based block copolymer (A ′ -5) was obtained.
- Comparative Example 6 Polymerization was carried out in the same manner as in Comparative Example 2 except that the solid titanium catalyst component ( ⁇ 2) was used and the residence time was 0.28 hours under the polymerization conditions of the gas phase polymerization vessel, and the propylene-based block copolymer (A ′ -6) was obtained.
- Example 4 With respect to 100 parts by weight of the propylene-based block copolymer (A-1) produced in Example 1, 0.3 part by weight of the crystal nucleating agent ADK STAB NA21 (trade name, Asahi Denka Co., Ltd.), heat resistance stabilizer IRGANOX 1010 (Ciba Geigy) (Trademark) 0.1 weight part, heat stabilizer IRGAFOS168 (Ciba-Geigy Corporation) 0.1 weight part, heat stabilizer IRGANOX1076 (Ciba-Geigy Corporation) 0.1 weight part, calcium stearate 0.1 After mixing the parts by weight with a tumbler, melt-kneaded with a twin-screw extruder in the same manner as in Example 1 to prepare a pellet-shaped polypropylene resin composition. did. Table 4 shows the mechanical properties and appearance of the molded product.
- Example 7 100 parts by weight of the propylene-based block copolymer (A′-1) produced in Comparative Example 1 was used instead of 100 parts by weight of the propylene-based block copolymer (A-1).
- a test piece was prepared in the same manner as in Example 4. Table 4 shows the mechanical properties and appearance of the molded product.
- Example 8 100 parts by weight of the propylene-based block copolymer (A′-2) produced in Comparative Example 2 was used instead of 100 parts by weight of the propylene-based block copolymer (A-1).
- a test piece was prepared in the same manner as in Example 4. Table 4 shows the mechanical properties and appearance of the molded product.
- Example 5 60 parts by weight of the propylene-based block copolymer (A-1) produced in Example 1, ethylene-butene copolymer rubber (Toughmer A1050 (trademark of Mitsui Chemicals)), talc (white filler 5000PJ ( Trademark), Matsumura Sangyo Co., Ltd.) 20 parts by weight, heat stabilizer IRGANOX 1010 (Ciba Geigy Co., Ltd.) 0.1 part by weight, heat stabilizer IRGAFOS168 (Ciba Geigy Co., Ltd.) 0.1 part by weight, heat stable 0.1 parts by weight of the agent IRGANOX 1076 (trademark of Ciba Geigy Co., Ltd.) and 0.1 parts by weight of calcium stearate were mixed with a tumbler, and melt-kneaded with a twin-screw extruder in the same manner as in Example 1 to form a pellet-shaped polypropylene resin Prepare the composition and create test pieces (ASTM test
- Example 9 In Example 5, 60 parts by weight of the propylene-based block copolymer (A′-1) produced in Comparative Example 1 was used instead of 60 parts by weight of the propylene-based block copolymer (A-1). A test piece was prepared in the same manner as in Example 5. Table 5 shows the mechanical properties and appearance of the molded product.
- Example 10 In Example 5, 60 parts by weight of the propylene-based block copolymer (A′-2) produced in Comparative Example 2 was used instead of 60 parts by weight of the propylene-based block copolymer (A-1). A test piece was prepared in the same manner as in Example 5. Table 5 shows the mechanical properties and appearance of the molded product.
- Example 6 (Preparation of solid titanium catalyst component ( ⁇ 2)) A 2 liter high-speed stirring device (made by Tokushu Kika Kogyo Co., Ltd. (TK homomixer M type)) was sufficiently purged with nitrogen, and then 700 ml of purified decane, 10 g of commercially available magnesium chloride, 24.2 g of ethanol, and the trade name Leodor SP- 3 g of S20 (sorbite distearate manufactured by Kao Corporation) was added, the system was heated while stirring this suspension, and the suspension was stirred at 120 ° C. and 800 rpm for 30 minutes. Next, 1 liter of purified decane that had been cooled to ⁇ 10 ° C.
- the solid part was collected by hot filtration, and the solid part was resuspended in 100 ml of titanium tetrachloride, and then heated to 110 ° C. and stirred for 45 minutes. These were allowed to react by holding. After completion of the reaction for 45 minutes, the solid part was again collected by hot filtration, and washed sufficiently with decane and heptane at 100 ° C. until no free titanium compound was detected in the washing solution.
- the solid titanium catalyst component ( ⁇ 2) prepared by the above operation was stored as a decane suspension, but a part of this was dried for the purpose of examining the catalyst composition.
- composition of the solid titanium catalyst component ( ⁇ 2) thus obtained was 3.2 mass% titanium, 17 mass% magnesium, 57 mass% chlorine, and diisobutyl 3,6-dimethylcyclohexane 1,2-dicarboxylate. It was 6% by mass, diisobutylcyclohexane 1,2-dicarboxylate 8.9% by mass and ethyl alcohol residue 0.6% by mass.
- Solid titanium catalyst component ( ⁇ 2) prepolymerization Solid titanium catalyst component ( ⁇ 2) prepolymerization
- dehydrated hexane was added to a three-necked flask equipped with a stirrer with an internal volume of 200 ml substituted with nitrogen, and 0.75 mmol of triethylaluminum and a suspension of the above solid titanium catalyst component ( ⁇ 2) were titanium.
- An amount of 0.25 mmol was added in terms of atoms, and the total amount was 50 ml.
- a predetermined amount of propylene was absorbed for 60 minutes while maintaining 20 ° C. Thereafter, the residual propylene was replaced with nitrogen and thoroughly washed with hexane to obtain a prepolymerized catalyst component (3 g-PP / g-solid titanium catalyst component).
- Dsol room temperature n-decane soluble part
- Dinsol room temperature n-decane insoluble part
- Table 6 shows the physical properties of the molded product.
- the obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A-5).
- the room temperature n-decane soluble part (Dsol) was 24.1% by weight, and the room temperature n-decane insoluble part (Dinsol) was 75.9% by weight.
- Example 8 (Main polymerization) The same operation as in Example 6 was performed except that the solid titanium catalyst component ( ⁇ 2) was used and hydrogenation was not performed in the gas phase. The obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A-6).
- the room temperature n-decane soluble part (Dsol) was 17.6% by weight, and the room temperature n-decane insoluble part (Dinsol) was 82.4% by weight.
- the mixture was heated to 80 ° C. over 5 hours, and when it reached 80 ° C., diisobutyl phthalate was added in an amount of 0.15 moles per mole of magnesium atoms in the solid adduct.
- the temperature was raised to 120 ° C. in 40 minutes. These were reacted by holding the temperature at 120 ° C. with stirring for 90 minutes.
- the solid part was collected by hot filtration, and the solid part was resuspended in 100 ml of titanium tetrachloride. These were reacted by holding them. After completion of the reaction for 45 minutes, the solid part was again collected by hot filtration, and washed sufficiently with decane and heptane at 100 ° C. until no free titanium compound was detected in the washing solution.
- the solid titanium catalyst component ( ⁇ 3) prepared by the above operation was stored as a decane suspension, but a part of this was dried for the purpose of examining the catalyst composition.
- composition of the solid titanium catalyst component ( ⁇ 3) thus obtained was 2.5% by mass of titanium, 20% by mass of magnesium, 58% by mass of chlorine, 9.5% by mass of diisobutyl phthalate, and ethyl alcohol residue 0 It was 1 mass%.
- Solid titanium catalyst component ( ⁇ 3) prepolymerization Solid titanium catalyst component ( ⁇ 3) prepolymerization
- dehydrated hexane was added to a three-necked flask equipped with a stirrer with an internal volume of 200 milliliters purged with nitrogen, and 0.75 mmol of triethylaluminum and a suspension of the above solid titanium catalyst component ( ⁇ 3) were titanium.
- An amount of 0.25 mmol was added in terms of atoms, and the total amount was 50 ml.
- a predetermined amount of propylene was absorbed for 60 minutes while maintaining 20 ° C. Thereafter, the residual propylene was replaced with nitrogen and thoroughly washed with hexane to obtain a prepolymerized catalyst component (3 g-PP / g-solid titanium catalyst component).
- Example 12 (Main polymerization) The same procedure as in Example 6 was performed, except that the solid titanium catalyst component ( ⁇ 3) was used and hydrogenation was not performed in the gas phase. The obtained polymer particles were dried under reduced pressure at room temperature overnight to obtain a propylene-based block copolymer (A′-8). (Molding) The propylene block copolymer (A′-8) was blended, granulated and injection molded in the same manner as in Example 6. Table 6 shows the physical properties of the molded product.
- the propylene-based block copolymer of the present invention and the composition containing the copolymer have high melt elasticity, excellent rigidity-impact resistance balance, and excellent workability, molded appearance, and molded product dimensional accuracy. Therefore, the present invention can be applied to reducing the thickness of automobile parts and industrial material parts, and reducing the weight of various molded articles such as foam molded articles and blow molded articles.
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Abstract
Description
[2]Dinsolの分子量分布(Mw/Mn)が7.0以上、30以下、Mz/Mwが6.0以上、20以下、
[3]Dinsolのペンタド分率(mmmm)が93%以上。
[5]DinsolのMz/Mnが70以上、300以下。
本発明のプロピレン系ブロック共重合体は、室温n-デカンに可溶な部分(Dsol)5~80重量%、好ましくは10~50重量%、さらに好ましくは10~30重量%と室温n-デカンに不溶な部分(Dinsol)20~95重量%、好ましくは50~90重量%、さらに好ましくは70~90重量%から構成される[ただし、DsolとDinsolの合計量は100重量%である]。
本発明に係るプロピレン系ブロック共重合体のデカン可溶部(Dsol)は、ゲルパーミエーションクロマトグラフィー(GPC)による測定値から求められる重量平均分子量(Mw)および数平均分子量(Mn)の比であるMw/Mn値が6.0~30であり、高流動性と高溶融張力の両立化の観点で、好ましくは6.5~20であり、より好ましくは7.0~18である。
本発明に係るプロピレン系ブロック共重合体のデカン不溶部(Dinsol)は、ゲルパーミエーションクロマトグラフィー(GPC)による測定値から求められるMw/Mn値が7.0~30であり、高剛性化と耐衝撃性の保持の観点で、好ましくは7.0~20であり、より好ましくは8.0~18である。
本発明のプロピレン系ブロック共重合体のデカン不溶部(Dinsol)のペンタド分率(mmmm)は93%以上、好ましくは94%以上、さらに好ましくは95%以上である。ペンタド分率の上限は100%、好ましくは99.8%、さらに好ましくは99.5%である。ペンタド分率(mmmm)が93%未満であると剛性が低下したり、フィルム等の製品分野で耐熱性が要求特性を担保しきれない分野があるので好ましくない。
本発明のプロピレン系ブロック共重合体のデカン可溶部(Dsol)の極限粘度[η](dl/g)は、通常1.5~10.0、耐衝撃性、高流動性、高溶融弾性のバランスを最適化させる観点で、好ましくは2.0~7.0、さらに好ましくは2.5~4.0の範囲である。極限粘度[η](dl/g)が、1.5dl/gよりも低下すると、プロピレン系ブロック共重合体の耐衝撃性が、低下するおそれがあるため、好ましくない。また、極限粘度[η](dl/g)が10dl/gよりも高いと、流動性の低下や、フィッシュアイが発生しやすくなるため、大型射出成形品やフィルムへの適用が難しくなる場合がある。
本発明に係るポリプロピレン系重合体のデカン不溶部(Dinsol)のMz/Mn値は、70~300であり、好ましくは100~250であり、より好ましくは120~200である。
本発明に係るプロピレン系ブロック共重合体は、固体状チタン触媒成分(I)と、周期表の第1族、第2族および第13族から選ばれる金属原子を含む有機金属化合物(II)と、必要に応じて電子供与体(III)とを含むオレフィン重合用触媒の存在下に重合して得られたものであることが好ましい。以下、オレフィン重合用触媒に係る各成分について詳細に説明する。
本発明に係る固体状チタン触媒成分(I)は、チタン、マグネシウム、ハロゲンおよび下記式(1)で特定される環状エステル化合物(a)と下記式(2)で特定される環状エステル化合物(b)を含む。
環状エステル化合物(a)は、複数のカルボン酸エステル基を有し、下記式(1)で表される。
3-メチルシクロヘキサン-1,2-ジカルボン酸ジエチル、
3-メチルシクロヘキサン-1,2-ジカルボン酸ジn-プロピル、
3-メチルシクロヘキサン-1,2-ジカルボン酸ジイソプロピル、
3-メチルシクロヘキサン-1,2-ジカルボン酸ジn-ブチル、
3-メチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3-メチルシクロヘキサン-1,2-ジカルボン酸ジヘキシル、
3-メチルシクロヘキサン-1,2-ジカルボン酸ジへプチル、
3-メチルシクロヘキサン-1,2-ジカルボン酸ジオクチル、
3-メチルシクロヘキサン-1,2-ジカルボン酸ジ2-エチルヘキシル、
3-メチルシクロヘキサン-1,2-ジカルボン酸ジデシル、
4-メチルシクロヘキサン-1,3-ジカルボン酸ジエチル、
4-メチルシクロヘキサン-1,3-ジカルボン酸ジイソブチル、
4-メチルシクロヘキサン-1,2-ジカルボン酸ジエチル、
4-メチルシクロヘキサン-1,2-ジカルボン酸ジn-プロピル、
4-メチルシクロヘキサン-1,2-ジカルボン酸ジイソプロピル、
4-メチルシクロヘキサン-1,2-ジカルボン酸ジn-ブチル、
4-メチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
4-メチルシクロヘキサン-1,2-ジカルボン酸ジヘキシル、
4-メチルシクロヘキサン-1,2-ジカルボン酸ジへプチル、
4-メチルシクロヘキサン-1,2-ジカルボン酸ジオクチル、
4-メチルシクロヘキサン-1,2-ジカルボン酸ジ2-エチルヘキシル、
4-メチルシクロヘキサン-1,2-ジカルボン酸ジデシル、
5-メチルシクロヘキサン-1,3-ジカルボン酸ジエチル、
5-メチルシクロヘキサン-1,3-ジカルボン酸ジイソブチル、
3,4-ジメチルシクロヘキサン-1,2-ジカルボン酸ジエチル、
3,4-ジメチルシクロヘキサン-1,2-ジカルボン酸ジn-プロピル、
3,4-ジメチルシクロヘキサン-1,2-ジカルボン酸ジイソプロピル、
3,4-ジメチルシクロヘキサン-1,2-ジカルボン酸ジn-ブチル、
3,4-ジメチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3,4-ジメチルシクロヘキサン-1,2-ジカルボン酸ジヘキシル、
3,4-ジメチルシクロヘキサン-1,2-ジカルボン酸ジへプチル、
3,4-ジメチルシクロヘキサン-1,2-ジカルボン酸ジオクチル、
3,4-ジメチルシクロヘキサン-1,2-ジカルボン酸ジ2-エチルヘキシル、
3,4-ジメチルシクロヘキサン-1,2-ジカルボン酸ジデシル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジエチル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジn-プロピル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジイソプロピル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジn-ブチル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジヘキシル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジへプチル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジオクチル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジ2-エチルヘキシル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジデシル、
3,6-ジフェニルシクロヘキサン-1,2-ジカルボン酸ジエチル、
3,6-ジフェニルシクロヘキサン-1,2-ジカルボン酸ジn-プロピル、
3,6-ジフェニルシクロヘキサン-1,2-ジカルボン酸ジイソプロピル、
3,6-ジフェニルシクロヘキサン-1,2-ジカルボン酸ジn-ブチル、
3,6-ジフェニルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3,6-ジフェニルシクロヘキサン-1,2-ジカルボン酸ジヘキシル、
3,6-ジフェニルシクロヘキサン-1,2-ジカルボン酸ジオクチル、
3,6-ジフェニルシクロヘキサン-1,2-ジカルボン酸ジデシル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジエチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジn-プロピル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジイソプロピル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジn-ブチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジヘキシル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジへプチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジオクチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジ2-エチルヘキシル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジデシル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジエチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジn-プロピル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジイソプロピル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジn-ブチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジヘキシル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジへプチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジオクチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジ2-エチルヘキシル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジデシル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジエチル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジn-プロピル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジイソプロピル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジn-ブチル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジヘキシル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジへプチル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジオクチル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジ2-エチルヘキシル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジデシル、
3-ヘキシルシクロヘキサン-1,2-ジカルボン酸ジエチル、
3-ヘキシルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3,6-ジヘキシルシクロヘキサン-1,2-ジカルボン酸ジエチル、
3-ヘキシル-6-ペンチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3-メチルシクロペンタン-1,2-ジカルボン酸ジエチル、
3-メチルシクロペンタン-1,2-ジカルボン酸ジイソブチル、
3-メチルシクロペンタン-1,2-ジカルボン酸ジへプチル、
3-メチルシクロペンタン-1,2-ジカルボン酸ジデシル、
4-メチルシクロペンタン-1,3-ジカルボン酸ジエチル、
4-メチルシクロペンタン-1,3-ジカルボン酸ジイソブチル、
4-メチルシクロペンタン-1,2-ジカルボン酸ジエチル、
4-メチルシクロペンタン-1,2-ジカルボン酸ジイソブチル、
4-メチルシクロペンタン-1,2-ジカルボン酸ジへプチル、
4-メチルシクロペンタン-1,2-ジカルボン酸ジデシル、
5-メチルシクロペンタン-1,3-ジカルボン酸ジエチル、
5-メチルシクロペンタン-1,3-ジカルボン酸ジイソブチル、
3,4-ジメチルシクロペンタン-1,2-ジカルボン酸ジエチル、
3,4-ジメチルシクロペンタン-1,2-ジカルボン酸ジイソブチル、
3,4-ジメチルシクロペンタン-1,2-ジカルボン酸ジへプチル、
3,4-ジメチルシクロペンタン-1,2-ジカルボン酸ジデシル、
3,5-ジメチルシクロペンタン-1,2-ジカルボン酸ジエチル、
3,5-ジメチルシクロペンタン-1,2-ジカルボン酸ジイソブチル、
3,5-ジメチルシクロペンタン-1,2-ジカルボン酸ジへプチル、
3,5-ジメチルシクロペンタン-1,2-ジカルボン酸ジデシル、
3-ヘキシルシクロペンタン-1,2-ジカルボン酸ジエチル、
3,5-ジヘキシルシクロペンタン-1,2-ジカルボン酸ジエチル、
3-ヘキシル-5-ペンチルシクロペンタン-1,2-ジカルボン酸ジイソブチル、
3-メチル-5-n-プロピルシクロペンタン-1,2-ジカルボン酸ジエチル、
3-メチル-5-n-プロピルシクロペンタン-1,2-ジカルボン酸ジn-プロピル、
3-メチル-5-n-プロピルシクロペンタン-1,2-ジカルボン酸ジイソプロピル、
3-メチル-5-n-プロピルシクロペンタン-1,2-ジカルボン酸ジn-ブチル、
3-メチル-5-n-プロピルシクロペンタン-1,2-ジカルボン酸ジイソブチル、
3-メチル-5-n-プロピルシクロペンタン-1,2-ジカルボン酸ジヘキシル、
3-メチル-5-n-プロピルシクロペンタン-1,2-ジカルボン酸ジオクチル、
3-メチル-5-n-プロピルシクロペンタン-1,2-ジカルボン酸ジデシル、
3-メチルシクロヘプタン-1,2-ジカルボン酸ジエチル、
3-メチルシクロヘプタン-1,2-ジカルボン酸ジイソブチル、
3-メチルシクロヘプタン-1,2-ジカルボン酸ジへプチル、
3-メチルシクロヘプタン-1,2-ジカルボン酸ジデシル、
4-メチルシクロヘプタン-1,3-ジカルボン酸ジエチル、
4-メチルシクロヘプタン-1,3-ジカルボン酸ジイソブチル、
4-メチルシクロヘプタン-1,2-ジカルボン酸ジエチル、
4-メチルシクロヘプタン-1,2-ジカルボン酸ジイソブチル、
4-メチルシクロヘプタン-1,2-ジカルボン酸ジへプチル、
4-メチルシクロヘプタン-1,2-ジカルボン酸ジデシル、
5-メチルシクロヘプタン-1,3-ジカルボン酸ジエチル、
5-メチルシクロヘプタン-1,3-ジカルボン酸ジイソブチル、
3,4-ジメチルシクロヘプタン-1,2-ジカルボン酸ジエチル、
3,4-ジメチルシクロヘプタン-1,2-ジカルボン酸ジイソブチル、
3,4-ジメチルシクロヘプタン-1,2-ジカルボン酸ジへプチル、
3,4-ジメチルシクロヘプタン-1,2-ジカルボン酸ジデシル、
3,7-ジメチルシクロヘプタン-1,2-ジカルボン酸ジエチル、
3,7-ジメチルシクロヘプタン-1,2-ジカルボン酸ジイソブチル、
3,7-ジメチルシクロヘプタン-1,2-ジカルボン酸ジへプチル、
3,7-ジメチルシクロヘプタン-1,2-ジカルボン酸ジデシル、
3-ヘキシルシクロヘプタン-1,2-ジカルボン酸ジエチル、
3,7-ジヘキシルシクロヘプタン-1,2-ジカルボン酸ジエチル、
3-ヘキシル-7-ペンチルシクロヘプタン-1,2-ジカルボン酸ジイソブチル、
3-メチル-7-n-プロピルシクロヘプタン-1,2-ジカルボン酸ジエチル、
3-メチル-7-n-プロピルシクロヘプタン-1,2-ジカルボン酸ジn-プロピル、
3-メチル-7-n-プロピルシクロヘプタン-1,2-ジカルボン酸ジイソプロピル、
3-メチル-7-n-プロピルシクロヘプタン-1,2-ジカルボン酸ジn-ブチル、
3-メチル-7-n-プロピルシクロヘプタン-1,2-ジカルボン酸ジイソブチル、
3-メチル-7-n-プロピルシクロヘプタン-1,2-ジカルボン酸ジヘキシル、
3-メチル-7-n-プロピルシクロヘプタン-1,2-ジカルボン酸ジオクチル、
3-メチル-7-n-プロピルシクロヘプタン-1,2-ジカルボン酸ジデシル、
3-メチルシクロオクタン-1,2-ジカルボン酸ジエチル、
3-メチルシクロデカン-1,2-ジカルボン酸ジエチル、
3-ビニルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3,6-ジフェニルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3,6-ジシクロヘキシルシクロヘキサン-1,2-ジカルボン酸ジエチル、
ノルボルナン-2,3-ジカルボン酸ジイソブチル、
テトラシクロドデカン-2,3-ジカルボン酸ジイソブチル、
3,6-ジメチル-4-シクロヘキセン-1,2-ジカルボン酸ジエチル、
3,6-ジメチル-4-シクロヘキセン-1,2-ジカルボン酸ジn-プロピル、
3,6-ジメチル-4-シクロヘキセン-1,2-ジカルボン酸ジイソプロピル、
3,6-ジメチル-4-シクロヘキセン-1,2-ジカルボン酸ジn-ブチル、
3,6-ジメチル-4-シクロヘキセン-1,2-ジカルボン酸ジイソブチル、
3,6-ジメチル-4-シクロヘキセン-1,2-ジカルボン酸ジヘキシル、
3,6-ジメチル-4-シクロヘキセン-1,2-ジカルボン酸ジへプチル、
3,6-ジメチル-4-シクロヘキセン-1,2-ジカルボン酸ジオクチル、
3,6-ジメチル-4-シクロヘキセン-1,2-ジカルボン酸ジ2-エチルヘキシル、
3,6-ジメチル-4-シクロヘキセン-1,2-ジカルボン酸ジデシル、
3,6-ジヘキシル-4-シクロヘキセン-1,2-ジカルボン酸ジエチル、
3-ヘキシル-6-ペンチル-4-シクロヘキセン-1,2-ジカルボン酸ジイソブチル、
などが挙げられる。
3,6-ジメチルシクロヘキサン-1,2-ジアセテート、
3,6-ジメチルシクロヘキサン-1,2-ジブタネート、
3-メチル-6-プロピルシクロヘキサン-1,2-ジオールアセテート、
3-メチル-6-プロピルシクロヘキサン-1,2-ジブタネート、
3,6-ジメチルシクロヘキサン-1,2-ジベンゾエート、
3,6-ジメチルシクロヘキサン-1,2-ジトルエート、
3-メチル-6-プロピルシクロヘキサン-1,2-ジベンゾエート、
3-メチル-6-プロピルシクロヘキサン-1,2-ジトルエート、
等も好ましい例として挙げることができる。
前記環状エステル化合物(a)としては、特には下記式(1a)で表わされる化合物が好ましい。
上記式(1a)で表わされる化合物として具体的には、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジn-ヘキシル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジn-オクチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジn-ヘキシル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジn-オクチル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジn-ヘキシル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジn-オクチル、
3,6-ジエチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3,6-ジエチルシクロヘキサン-1,2-ジカルボン酸ジn-ヘキシル、
3,6-ジエチルシクロヘキサン-1,2-ジカルボン酸ジn-オクチル、
3,5-ジメチルシクロペンタン-1,2-ジカルボン酸ジイソブチル、
3,5-ジメチルシクロペンタン-1,2-ジカルボン酸ジn-ヘキシル、
3,5-ジメチルシクロペンタン-1,2-ジカルボン酸ジn-オクチル、
3-メチル-5-エチルシクロペンタン-1,2-ジカルボン酸ジイソブチル、
3-メチル-5-エチルシクロペンタン-1,2-ジカルボン酸ジn-ヘキシル、
3-メチル-5-エチルシクロペンタン-1,2-ジカルボン酸ジn-オクチル、
3-メチル-5-n-プロピルシクロペンタン-1,2-ジカルボン酸ジn-ヘキシル、
3-メチル-5-n-プロピルシクロペンタン-1,2-ジカルボン酸ジn-オクチル、
3,5-ジエチルシクロペンタン-1,2-ジカルボン酸ジイソブチル、
3,5-ジエチルシクロペンタン-1,2-ジカルボン酸ジn-ヘキシル、
3,5-ジエチルシクロペンタン-1,2-ジカルボン酸ジn-オクチル、
3,7-ジメチルシクロヘプタン-1,2-ジカルボン酸ジイソブチル、
3,7-ジメチルシクロヘプタン-1,2-ジカルボン酸ジn-ヘキシル、
3,7-ジメチルシクロヘプタン-1,2-ジカルボン酸ジn-オクチル、
3-メチル-7-エチルシクロヘプタン-1,2-ジカルボン酸ジイソブチル、
3-メチル-7-エチルシクロヘプタン-1,2-ジカルボン酸ジn-ヘキシル、
3-メチル-7-エチルシクロヘプタン-1,2-ジカルボン酸ジn-オクチル、
3-メチル-7-n-プロピルシクロヘプタン-1,2-ジカルボン酸ジn-ヘキシル、
3-メチル-7-n-プロピルシクロヘプタン-1,2-ジカルボン酸ジn-オクチル、
3,7-ジエチルシクロヘプタン-1,2-ジカルボン酸ジイソブチル、
3,7-ジエチルシクロヘプタン-1,2-ジカルボン酸ジn-ヘキシル、
3,7-ジエチルシクロヘプタン-1,2-ジカルボン酸ジn-オクチル、
などが挙げられる。
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジn-ヘキシル、
3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジn-オクチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジn-ヘキシル、
3-メチル-6-エチルシクロヘキサン-1,2-ジカルボン酸ジn-オクチル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジn-ヘキシル、
3-メチル-6-n-プロピルシクロヘキサン-1,2-ジカルボン酸ジn-オクチル、
3,6-ジエチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル、
3,6-ジエチルシクロヘキサン-1,2-ジカルボン酸ジn-ヘキシル、
3,6-ジエチルシクロヘキサン-1,2-ジカルボン酸ジn-オクチル
がさらに好ましい。これらの化合物はDiels Alder反応を利用して製造できる。
環状エステル化合物(b)は、複数のカルボン酸エステル基を有し、下記式(2)で表される。
シクロヘキサン-1,2-ジカルボン酸ジエチル、
シクロヘキサン-1,2-ジカルボン酸ジn-プロピル、
シクロヘキサン-1,2-ジカルボン酸ジイソプロピル、
シクロヘキサン-1,2-ジカルボン酸ジn-ブチル、
シクロヘキサン-1,2-ジカルボン酸ジイソブチル、
シクロヘキサン-1,2-ジカルボン酸ジヘキシル、
シクロヘキサン-1,2-ジカルボン酸ジへプチル、
シクロヘキサン-1,2-ジカルボン酸ジオクチル、
シクロヘキサン-1,2-ジカルボン酸ジ2-エチルヘキシル、
シクロヘキサン-1,2-ジカルボン酸ジデシル、
シクロヘキサン-1,3-ジカルボン酸ジエチル、
シクロヘキサン-1,3-ジカルボン酸ジイソブチル、
シクロペンタン-1,2-ジカルボン酸ジエチル、
シクロペンタン-1,2-ジカルボン酸ジイソプロピル、
シクロペンタン-1,2-ジカルボン酸ジイソブチル、
シクロペンタン-1,2-ジカルボン酸ジへプチル、
シクロペンタン-1,2-ジカルボン酸ジデシル、
シクロペンタン-1,3-ジカルボン酸ジエチル、
シクロペンタン-1,3-ジカルボン酸ジイソブチル、
シクロヘプタン-1,2-ジカルボン酸ジエチル、
シクロヘプタン-1,2-ジカルボン酸ジイソプロピル、
シクロヘプタン-1,2-ジカルボン酸ジイソブチル、
シクロヘプタン-1,2-ジカルボン酸ジへプチル、
シクロヘプタン-1,2-ジカルボン酸ジデシル、
シクロヘプタン-1,3-ジカルボン酸ジエチル、
シクロヘプタン-1,3-ジカルボン酸ジイソブチル、
シクロオクタン-1,2-ジカルボン酸ジエチル、
シクロデカン-1,2-ジカルボン酸ジエチル、
4-シクロヘキセン-1,2-ジカルボン酸ジエチル、
4-シクロヘキセン-1,2-ジカルボン酸ジn-プロピル、
4-シクロヘキセン-1,2-ジカルボン酸ジイソプロピル、
4-シクロヘキセン-1,2-ジカルボン酸ジn-ブチル、
4-シクロヘキセン-1,2-ジカルボン酸ジイソブチル、
4-シクロヘキセン-1,2-ジカルボン酸ジヘキシル、
4-シクロヘキセン-1,2-ジカルボン酸ジへプチル、
4-シクロヘキセン-1,2-ジカルボン酸ジオクチル、
4-シクロヘキセン-1,2-ジカルボン酸ジデシル、
4-シクロヘキセン-1,3-ジカルボン酸ジエチル、
4-シクロヘキセン-1,3-ジカルボン酸ジイソブチル、
3-シクロペンテン-1,2-ジカルボン酸ジエチル、
3-シクロペンテン-1,2-ジカルボン酸ジイソプロピル、
3-シクロペンテン-1,2-ジカルボン酸ジイソブチル、
3-シクロペンテン-1,2-ジカルボン酸ジへプチル、
3-シクロペンテン-1,2-ジカルボン酸ジデシル、
3-シクロペンテン-1,3-ジカルボン酸ジエチル、
3-シクロペンテン-1,3-ジカルボン酸ジイソブチル、
4-シクロヘプテン-1,2-ジカルボン酸ジエチル、
4-シクロヘプテン-1,2-ジカルボン酸ジイソプロピル、
4-シクロヘプテン-1,2-ジカルボン酸ジイソブチル、
4-シクロヘプテン-1,2-ジカルボン酸ジへプチル、
4-シクロヘプテン-1,2-ジカルボン酸ジデシル、
4-シクロヘプテン-1,3-ジカルボン酸ジエチル、
4-シクロヘプテン-1,3-ジカルボン酸ジイソブチル、
5-シクロオクテン-1,2-ジカルボン酸ジエチル、
6-シクロデセン-1,2-ジカルボン酸ジエチル、
などが挙げられる。
シクロヘキサン-1,2-ジアセテート、
シクロヘキサン-1,2-ジブタネート、
シクロヘキサン-1,2-ジベンゾエート、
シクロヘキサン-1,2-ジトルエート、
なども好ましい例として挙げることができる。
上記式(2a)で表わされる化合物として具体的には、
シクロヘキサン-1,2-ジカルボン酸ジn-ブチル、
シクロヘキサン-1,2-ジカルボン酸ジイソブチル、
シクロヘキサン-1,2-ジカルボン酸ジヘキシル、
シクロヘキサン-1,2-ジカルボン酸ジへプチル、
シクロヘキサン-1,2-ジカルボン酸ジオクチル、
シクロヘキサン-1,2-ジカルボン酸ジ2-エチルヘキシル、
シクロペンタン-1,2-ジカルボン酸ジイソブチル、
シクロペンタン-1,2-ジカルボン酸ジヘプチル、
シクロヘプタン-1,2-ジカルボン酸ジイソブチル、
シクロヘプタン-1,2-ジカルボン酸ジへプチル
などが挙げられる。
シクロヘキサン-1,2-ジカルボン酸ジイソブチル、
シクロヘキサン-1,2-ジカルボン酸ジヘキシル、
シクロヘキサン-1,2-ジカルボン酸ジへプチル、
シクロヘキサン-1,2-ジカルボン酸ジオクチル、
シクロヘキサン-1,2-ジカルボン酸ジ2-エチルヘキシル、
がさらに好ましい。その理由は、触媒性能だけでなく、これらの化合物がDiels Alder反応を利用して比較的安価に製造できる点にある。
本発明に係る固体状チタン触媒成分(I)の調製に用いられるマグネシウム化合物として具体的には、
塩化マグネシウム、臭化マグネシウムなどのハロゲン化マグネシウム;
メトキシ塩化マグネシウム、エトキシ塩化マグネシウム、フェノキシ塩化マグネシウムなどのアルコキシマグネシウムハライド;
エトキシマグネシウム、イソプロポキシマグネシウム、ブトキシマグネシウム、2-エチルヘキソキシマグネシウムなどのアルコキシマグネシウム;
フェノキシマグネシウムなどのアリーロキシマグネシウム;
ステアリン酸マグネシウムなどのマグネシウムのカルボン酸塩などの公知のマグネシウム化合物を挙げることができる。
チタン化合物としては、例えば一般式;
Ti(OR)gX4-g
(Rは炭化水素基であり、Xはハロゲン原子であり、gは0≦g≦4である。)
で示される4価のチタン化合物を挙げることができる。より具体的には、
TiCl4、TiBr4などのテトラハロゲン化チタン;
Ti(OCH3)Cl3、Ti(OC2H5)Cl3、Ti(O-n-C4H9)Cl3、Ti(OC2H5)Br3、Ti(O-isoC4H9)Br3などのトリハロゲン化アルコキシチタン;
Ti(OCH3)2Cl2、Ti(OC2H5)2Cl2などのジハロゲン化アルコキシチタン;
Ti(OCH3)3Cl、Ti(O-n-C4H9)3Cl、Ti(OC2H5)3Brなどのモノハロゲン化アルコキシチタン;
Ti(OCH3)4、Ti(OC2H5)4、Ti(OC4H9)4、Ti(O-2-エチルヘキシル)4などのテトラアルコキシチタンなどを挙げることができる。
上記の固体状付加物や液状状態のマグネシウム化合物の形成に用いられる触媒成分(c)としては、室温~300℃程度の温度範囲で上記のマグネシウム化合物を可溶化できる公知の化合物が好ましく、例えばアルコール、アルデヒド、アミン、カルボン酸およびこれらの混合物などが好ましい。これらの化合物としては、例えば前記特許文献1や特許文献2に詳細に記載されている化合物を挙げることができる。
メタノール、エタノール、プロパノール、ブタノール、イソブタノール、エチレングリコール、2-メチルペンタノール、2-エチルブタノール、n-ヘプタノール、n-オクタノール、2-エチルヘキサノール、デカノール、ドデカノールのような脂肪族アルコール;
シクロヘキサノール、メチルシクロヘキサノールのような脂環族アルコール;
ベンジルアルコール、メチルベンジルアルコールなどの芳香族アルコール;
n-ブチルセルソルブなどのアルコキシ基を有する脂肪族アルコールなどを挙げることができる。
本発明の固体状チタン触媒成分(I)は、さらに、芳香族カルボン酸エステルおよび/または複数の炭素原子を介して2個以上のエーテル結合を有する化合物(以下「触媒成分(d)」ともいう。)を含んでいてもよい。本発明の固体状チタン触媒成分(I)が触媒成分(d)を含んでいると触媒活性を向上させたり、立体規則性を高めたり、分子量分布をより広げることができる場合がある。
2-イソプロピル-1,3-ジメトキシプロパン、
2-s-ブチル-1,3-ジメトキシプロパン、
2-クミル-1,3-ジメトキシプロパン
等の1置換ジアルコキシプロパン類、
2-イソプロピル-2-イソブチル-1,3-ジメトキシプロパン、
2,2-ジシクロヘキシル-1,3-ジメトキシプロパン、
2-メチル-2-イソプロピル-1,3-ジメトキシプロパン、
2-メチル-2-シクロヘキシル-1,3-ジメトキシプロパン、
2-メチル-2-イソブチル-1,3-ジメトキシプロパン、
2,2-ジイソブチル-1,3-ジメトキシプロパン、
2,2-ビス(シクロヘキシルメチル)-1,3-ジメトキシプロパン、
2,2-ジイソブチル-1,3-ジエトキシプロパン、
2,2-ジイソブチル-1,3-ジブトキシプロパン、
2,2-ジ-s-ブチル-1,3-ジメトキシプロパン、
2,2-ジネオペンチル-1,3-ジメトキシプロパン、
2-イソプロピル-2-イソペンチル-1,3-ジメトキシプロパン、
2-シクロヘキシル-2-シクロヘキシルメチル-1,3-ジメトキシプロパン
等の2置換ジアルコキシプロパン類、
2,3-ジシクロヘキシル-1,4-ジメトキシブタン、
2,3-ジシクロヘキシル-1,4-ジエトキシブタン、
2,3-ジイソプロピル-1,4-ジエトキシブタン、
2,4-ジフェニル-1,5-ジメトキシペンタン、
2,5-ジフェニル-1,5-ジメトキシヘキサン、
2,4-ジイソプロピル-1,5-ジメトキシペンタン、
2,4-ジイソブチル-1,5-ジメトキシペンタン、
2,4-ジイソアミル-1,5-ジメトキシペンタン
等のジアルコキシアルカン類、
2-メチル-2-メトキシメチル-1,3-ジメトキシプロパン、
2-シクロヘキシル-2-エトキシメチル-1,3-ジエトキシプロパン、
2-シクロヘキシル-2-メトキシメチル-1,3-ジメトキシプロパン
等のトリアルコキシアルカン類、
2,2-ジイソブチル-1,3-ジメトキシ4-シクロヘキセン、
2-イソプロピル-2-イソアミル-1,3-ジメトキシ4-シクロヘキセン、
2-シクロヘキシル-2-メトキシメチル-1,3-ジメトキシ4-シクロヘキセン、
2-イソプロピル-2-メトキシメチル-1,3-ジメトキシ4-シクロヘキセン、
2-イソブチル-2-メトキシメチル-1,3-ジメトキシ4-シクロヘキセン、
2-シクロヘキシル-2-エトキシメチル-1,3-ジメトキシ4-シクロヘキセン、
2-イソプロピル-2-エトキシメチル-1,3-ジメトキシ4-シクロヘキセン、
2-イソブチル-2-エトキシメチル-1,3-ジメトキシ4-シクロヘキセン
等のジアルコキシシクロアルカン
等を例示することができる。
環状エステル化合物(a)/チタン(モル比)(すなわち、環状エステル化合物(a)のモル数/チタン原子のモル数)および環状エステル化合物(b)/チタン(モル比)(すなわち、環状エステル化合物(b)のモル数/チタン原子のモル数)は、0.01~100、好ましくは0.2~10であることが望ましく、
触媒成分(c)は、触媒成分(c)/チタン原子(モル比)は0~100、好ましくは0~10であることが望ましい。
有機金属化合物触媒成分(II)としては、周期表の第1族、第2族および第13族から選ばれる金属原子を含む有機金属化合物が挙げられる。具体的には、第13族金属を含む化合物、例えば、有機アルミニウム化合物、第1族金属とアルミニウムとの錯アルキル化物、第2族金属の有機金属化合物などを用いることができる。これらの中でも有機アルミニウム化合物が好ましい。
また、本発明のオレフィン重合用触媒は、上記の有機金属化合物触媒成分(II)と共に、必要に応じて電子供与体(III)を含んでいてもよい。電子供与体(III)として好ましくは、有機ケイ素化合物が挙げられる。この有機ケイ素化合物としては、例えば下記一般式(4)で表される化合物を例示できる。
(式中、RおよびR’は炭化水素基であり、nは0<n<4の整数である。)
上記のような一般式(4)で示される有機ケイ素化合物としては、具体的には、ジイソプロピルジメトキシシラン、t-ブチルメチルジメトキシシラン、t-ブチルメチルジエトキシシラン、t-アミルメチルジエトキシシラン、ジシクロヘキシルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、シクロヘキシルメチルジエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、t-ブチルトリエトキシシラン、フェニルトリエトキシシラン、シクロヘキシルトリメトキシシラン、シクロペンチルトリメトキシシラン、2-メチルシクロペンチルトリメトキシシラン、シクロペンチルトリエトキシシラン、ジシクロペンチルジメトキシシラン、ジシクロペンチルジエトキシシラン、トリシクロペンチルメトキシシラン、ジシクロペンチルメチルメトキシシラン、ジシクロペンチルエチルメトキシシラン、シクロペンチルジメチルエトキシシランなどが用いられる。
式(5)中、Raは、炭素原子数1~6の炭化水素基であり、好ましくは、炭素原子数1~6の不飽和あるいは飽和脂肪族炭化水素基などが挙げられ、特に好ましくは炭素原子数2~6の飽和脂肪族炭化水素基が挙げられる。具体例としてはメチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、n-ペンチル基、iso-ペンチル基、シクロペンチル基、n-ヘキシル基、シクロヘキシル基等が挙げられ、これらの中でもエチル基が特に好ましい。
ジメチルアミノトリエトキシシラン、
ジエチルアミノトリエトキシシラン、
ジメチルアミノトリメトキシシラン、
ジエチルアミノトリメトキシシラン、
ジエチルアミノトリn-プロポキシシラン、
ジ-n-プロピルアミノトリエトキシシラン、
メチル-n-プロピルアミノトリエトキシシラン、
t-ブチルアミノトリエトキシシラン、
エチル-n-プロピルアミノトリエトキシシラン、
エチル-iso-プロピルアミノトリエトキシシラン、
メチルエチルアミノトリエトキシシラン
が挙げられる。
式(6)中、RNは、環状アミノ基であり、この環状アミノ基として、例えば、パーヒドロキノリノ基、パーヒドロイソキノリノ基、1,2,3,4-テトラヒドロキノリノ基、1,2,3,4-テトラヒドロイソキノリノ基、オクタメチレンイミノ基等が挙げられる。Raは、式(5)で定義したものと同様のものが挙げられる。上記式(6)で表される化合物として具体的には、
(パーヒドロキノリノ)トリエトキシシラン、
(パーヒドロイソキノリノ)トリエトキシシラン、
(1,2,3,4-テトラヒドロキノリノ)トリエトキシシラン、
(1,2,3,4-テトラヒドロイソキノリノ)トリエトキシシラン、
オクタメチレンイミノトリエトキシシラン
等が挙げられる。
本発明に係るプロピレン系ブロック共重合体は、前記要件[1]~[3]および好ましくは要件[4]および/または[5]を満たす限り製造方法が限定されるものではない。
プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、灯油などの脂肪族炭化水素;
シクロペンタン、メチルシクロペンタン、シクロヘキサン、シクロヘプタン、メチルシクロヘプタン、シクロオクタンなどの脂環族炭化水素;
ベンゼン、トルエン、キシレンなどの芳香族炭化水素;
エチレンクロリド、クロルベンゼンなどのハロゲン化炭化水素;
あるいはこれらの混合物などを挙げることができる。
次の二つの重合工程(重合工程1および重合工程2)を連続的に実施することによって、要件[1]~要件[3]および好ましくは要件[4]および/または[5]を満たすプロピレン系ブロック共重合体を製造する方法(以下、この方法を「直重法」と呼び、この方法によって得られるプロピレン系ブロック共重合体を、プロピレン系ブロック共重合体(A)と呼ぶ場合がある)。
前記方法Aの重合工程1で生成する(共)重合体と、前記方法Aの重合工程2で生成する共重合体を、固体状チタン触媒成分の存在下で個別に製造した後に、これらを物理的手段によりブレンドする方法(以下、この方法「ブレンド法」と呼び、この方法によって得られるプロピレン系ブロック共重合体を、プロピレン系共重合体(B)と呼ぶ場合がある)。
本発明に係るプロピレン樹脂組成物は、本発明に係るプロピレン系ブロック共重合体と、以下に示す各種添加剤などとを、好ましくは無機充填剤および/またはエラストマーとを混合したものである。
本発明で用いられる安定剤は、耐熱安定剤、耐候安定剤、耐光安定剤、塩化吸収剤、充填剤、結晶核剤、軟化剤等の公知の安定剤を制限無く用いることができる。例えば公知のフェノール系安定剤、有機ホスファイト系安定剤、チオエーテル系安定剤、ヒンダードアミン系安定剤、ステアリン酸カルシウムなどの高級脂肪酸金属塩、無機酸化物、ガラス繊維などが挙げられる。
本発明に係るポリプロピレン樹脂組成物には、さらに、他の耐熱安定剤、耐候安定剤、帯電防止剤、スリップ剤、アンチブロッキング剤、防曇剤、滑剤、染料、顔料、天然油、合成油、ワックスなどを含んでいてもよい。
前記プロピレン系ブロック共重合体からなる樹脂成形体としては、射出成形体、発泡成形体、射出発泡成形体、押出成形体、ブロー成形体、真空・圧空成形体、カレンダー成形体、延伸フィルム、インフレーションフィルムなどが挙げられる。
本発明に係る射出成形体は剛性と低温耐衝撃性のバランスに優れ、さらにフローマーク、ブツ等の不具合が無い等、成形体外観が良好である。したがって、本発明に係る射出成形体は用途が限定されることはないが、特にバンパー、サイドモール、フェンダー、アンダーカバー等の自動車外装部品、インストルメントパネル、ドアトリム、ピラー等の自動車内装部品、エンジンルーム周辺部品、その他自動車部品、家電部品、食品容器、飲料容器、医療容器、コンテナ等に好適に使用することができる。
本発明の発泡成形体は、本発明のプロピレン系ブロック共重合体と、発泡剤と、必要に応じて有機過酸化物と、架橋助剤などを含んでなる発泡体成形用樹脂組成物を加熱することによって製造することができる。
本発明のプロピレン系ブロック共重合体は、溶融張力が高く、剛性と耐衝撃性とのバランスに優れることから、本発明のプロピレン系ブロック共重合体より、高発泡倍率で、表面外観が良好かつ機械強度に優れた射出発泡成形体を得ることができる。
本発明に係る押出成形体は、本発明のプロピレン系ブロック共重合体を用いて押出法で成形することによって製造される。前記プロピレン系ブロック共重合体は高いメルトテンションを有しているため、押出成形時に高速で成形することができたり、大型の製品を得ることができる。
本発明に係るブロー成形体は、本発明のプロピレン系ブロック共重合体を用いてブロー法で成形することによって製造される。前記プロピレン系ブロック共重合体は高いメルトテンションを有しているため、ブロー成形時に高速成形が可能であったり、大型の製品を得ることができる。
本発明に係る真空・圧空成形体は、本発明のプロピレン系ブロック共重合体からなるシートを真空成形法あるいは圧空成形法で成形することにより製造される。前記プロピレン系ブロック共重合体は高いメルトテンションを有しているため、シートは充分に金型形状に沿って変形する。したがって、本発明に係る真空・圧空成形体は、製品の大型化が可能であり、また深絞りが可能である。
本発明に係るカレンダー成形体は、本発明のプロピレン系ブロック共重合体を用いてカレンダー法で成形することによって製造される。前記プロピレン系ブロック共重合体は高いメルトテンションを有しているため、厚みむらが少ないフィルムを得ることができる。
本発明に係る延伸フィルムは、本発明のプロピレン系ブロック共重合体を用いて延伸法で成形することによって製造される。前記プロピレン系ブロック共重合体は高いメルトテンションを有しているため、成形安定性に優れ、かつ高速で成形することができる。
本発明に係るインフレーションフィルムは、本発明のプロピレン系ブロック共重合体を用いてインフレーション法で成形することによって製造される。前記プロピレン系ブロック共重合体は高いメルトテンションを有しているため、成形時にバブルが安定しており、製造時に形成速度を高めることができる。
本発明のプロピレン系ブロック共重合体からなる成形体は、上記各成形体の他にもスタンピングモールド成形法など公知の成形法を用いて得ることができる。
ASTM D1238Eに準拠し、2.16kg荷重で測定した。測定温度は230℃とした。
重合体粒子をデカリンに溶解させ、温度135℃のデカリン中で常法に従い測定した。
ガラス製の測定容器にプロピレン系ブロック共重合体約3g(10-4gの単位まで測定した。また、この重量を、下式においてb(g)と表した。)、デカン500ml、およびデカンに可溶な耐熱安定剤を少量装入し、窒素雰囲気下、スターラーで攪拌しながら2時間で150℃に昇温してプロピレン系ブロック共重合体を溶解させ、150℃で2時間保持した後、8時間かけて23℃まで徐冷した。得られたプロピレン系ブロック共重合体の析出物を含む液を、磐田ガラス社製25G-4規格のグラスフィルターで減圧ろ過した。ろ液の100mlを採取し、これを減圧乾燥してデカン可溶成分の一部を得、この重量を10-4gの単位まで測定した(この重量を、下式においてa(g)と表した)。この操作の後、デカン可溶成分量を下記式によって決定した。
室温n-デカン不溶成分(Dinsol)含有率=100-100×(500×a)/(100×b)
(4)分子量分布:
液体クロマトグラフ:Waters製 ALC/GPC 150-C plus型 (示唆屈折計検出器一体型)
カラム:東ソー株式会社製 GMH6-HT×2本およびGMH6-HTL×2本を直列接続した。
流速:1.0ml/分
測定温度:140℃
検量線の作成方法:標準ポリスチレンサンプルを使用した
サンプル濃度:0.10%(w/w)
サンプル溶液量:500μl
の条件で測定し、得られたクロマトグラムを公知の方法によって解析することでMw/Mn値、Mz/Mw値およびMz/Mn値を算出した。1サンプル当たりの測定時間は60分であった。
重合体の立体規則性の指標の1つであり、そのミクロタクティシティーを調べたペンタド分率(mmmm:〔%〕)は、プロピレン重合体においてMacromolecules 8,687(1975)に基づいて帰属した13C-NMRスペクトルのピーク強度比より算出した。13C-NMRスペクトルは、日本電子製EX-400の装置を用い、TMSを基準とし、温度130℃、o-ジクロロベンゼン溶媒を用いて測定した。
(ASTM試験片)
曲げ弾性率(FM:〔MPa〕)は、ASTM D790に従って、下記の条件で測定した。
試験片:12.7mm(幅)×6.4mm(厚さ)×127mm(長さ)
曲げ速度:2.8mm/分
曲げスパン:100mm
(JIS小型試験片)
曲げ弾性率(FM:〔MPa〕)は、JIS K7171に従って、下記の条件で測定した。
試験片 : 10mm(幅)×4mm(厚さ)×80mm(長さ)
曲げ速度 : 2mm/分
曲げスパン : 64mm
(7)Izod衝撃強度
(ASTM試験片)
アイゾット衝撃強度(IZ:〔J/m〕)は、ASTM D256に準拠して下記の条件で測定した。
温度:23℃、-30℃
試験片:12.7mm(幅)×6.4mm(厚さ)×64mm(長さ)
ノッチは機械加工
(8)シャルピー衝撃試験
(JIS小型試験片)
シャルピー衝撃試験(〔kJ/m2〕)は、JIS K7111に従って、下記の条件で測定した。
温度:23℃、-30℃
試験片 : 10mm(幅)×4mm(厚さ)×80mm(長さ)
ノッチは機械加工
(9)引張り破断伸び
(ASTM試験片)
引張り破断伸び(EL:〔%〕)は、ASTM D638に従って測定した。
試験片:ASTM-1号ダンベル
19mm(幅)×3.2mm(厚さ)×165mm(長さ)
引張速度:50mm/分
スパン間距離:115mm
(JIS小型試験片)
引張り破断伸び(EL:〔%〕)は、JIS K7162-BAに従って測定した。
試験片 : JIS K7162-BAダンベル
5mm(幅)×2mm(厚さ)×75mm(長さ)
引張速度 : 20mm/分
スパン間距離 : 58mm
(10)加熱変形温度
(ASTM試験片)
加熱変形温度(HDT:〔℃〕)は、ASTM D648に従って測定した。
試験片:12.7mm(幅)×6.4mm(厚さ)×127mm(長さ)
荷重:0.45MPa
試験片の厚み:1/4インチ
(JIS小型試験片)
加熱変形温度(HDT:〔℃〕)は、JIS K7191に従って、下記の条件で測定した。
<測定条件>
試験片: 10mm(幅)×4mm(厚さ)×80mm(長さ)
荷重 : 0.45MPa
(11)スウェル
スウェルは、キャピログラフ((株)東洋精機製)を用いて、下記に従って測定した。
キャピラリー長:20mm
キャピラリー径:1mm
測定温度:230℃
剪断速度:1216sec-1
(12)外観フローマーク
射出成形品のフローマークは、長さ350mm、幅100mm、厚み3mmの平板が成形可能で中央部(50mm)にゲートを持つ射出成形金型を用いた(図1)。ここで、ゲートからフローマークが発生した面積を目視で評価した。
射出成形機:品番 M200、名機製作所(株)製
シリンダー温度:210℃
金型温度:40℃
成形品形状:図1に示す。
(13)フィッシュアイ
25mmφTダイ押出機[(株)シンコーマシーナリー社製]にてキャストフィルムを製膜し、直径200μm以上のフィッシュアイの個数を測定した。
押出温度:250℃
チルロール温度:40℃
フィルム厚さ:50μm
スクリーンメッシュ:スクリーンメッシュ#60を1枚
(14)固体粘弾性tanδ測定(〔℃〕)
ペレットをプレス成形して成形品を作成し、固体粘弾性測定装置で温度分散測定を行った。プロピレン-エチレンおよび/またはα-オレフィン共重合体ゴム部のガラス転移温度指標として、-30℃以下でのtanδピーク温度を読み取った。
測定装置 :RSA-II(TA製)
測定モード:引張モード(Autotension,Autostrain制御)
測定温度 :-80~150℃(測定可能な温度まで)
昇温速度 :3℃/min
測定周波数:1Hz
試料サイズ:幅5mm×厚さ0.4mm
初期Gap(L0):21.5mm
雰囲気 :N2
(15)メルトテンション
メルトテンション(MT:〔g〕)は、メルトテンション測定装置(東洋精機製作所(株)製)を用いて、オリフィス(L=8.00mm、D=2.095mm)、設定温度230℃、ピストン降下速度15mm/分、巻取り速度15mm/分の条件で、ロードセル検出付きプーリーの巻取り荷重を測定した値である。
線膨張係数測定は、TMA測定装置((株)TAインストルメント社製、TMA2940)を用いて、下記試験条件にて行った。
試験温度範囲 : -40~110℃
試験荷重 : 0.029N(3g)(プローブ:約3mmφ)
昇温速度 : 5℃/min
測定方向 : 射出成形体のMD(Machine Direction)方向(流れ方向)、およびTD(Transverse Direction)方向(垂直方向)
アニール処理 : 無し
試験片 :角板(100mm(幅)×100mm(長さ)×2mm(厚さ))、小型角板(30mm(幅)×30mm(長さ)×2mm(厚さ))
[実施例1]
(固体状チタン触媒成分(α1)の調製)
無水塩化マグネシウム75g、デカン280.3gおよび2-エチルヘキシルアルコール308.3gを130℃で3時間加熱反応させて均一溶液とした後、この溶液中にエチルベンゾエート17.7gを添加し、さらに130℃にて1時間攪拌混合を行った。
窒素で置換した内容積2リットルの攪拌機付きの三つ口フラスコに、上記の固体状チタン触媒成分(α1)120グラム(75.2ミリモル-Ti)を含むヘプタンスラリーを投入し、さらに、脱水したヘプタンを加えて、全量を1リットルとした。これを20℃以下に制御しながら攪拌し、トリエチルアルミニウム226ミリモルを加えた。20℃のまま、120分間プロピレンを所定量吸収させ、残留プロピレンを窒素で置換して、ヘプタンを用いて充分洗浄を行い、予備重合触媒成分を1.3kg得た(10g-PP/g-固体状チタン触媒成分)。
内容量58Lの環状重合器にプロピレンを43kg/hr、水素を160NL/hr、触媒スラリーを固体触媒成分として0.50g/hr、トリエチルアルミニウム2.16mL/hr、ジシクロペンチルジメトキシシラン2.2mL/hrを連続的に供給し、気相の存在しない満液の状態にて重合した。環状反応器の温度は70℃であり、圧力は3.5MPa/Gであった。
プロピレン系ブロック共重合体(A-1)100重量部に対して、耐熱安定剤IRGANOX1010(チバジャパン(株)商標)0.1重量部、耐熱安定剤IRGAFOS168(チバジャパン(株)商標)0.1重量部、耐熱安定剤IRGANOX1076(チバジャパン(株)商標)0.1重量部、ステアリン酸カルシウム0.1重量部をタンブラーにて混合後、二軸押出機にて溶融混練してペレット状のポリプロピレン樹脂組成物を調製し、射出成形機にて試験片(ASTM試験片、線膨張係数測定用角板)した。成形品の物性および射出成形品外観、射出成形流動性の評価結果を表1に示す。また、フローマーク評価に用いた射出成形体の写真を図2に示す。
同方向二軸混練機:品番 NR2-36、ナカタニ機械(株)製
混練温度:230℃
スクリュー回転数:200rpm
フィーダー回転数:500rpm
ホッパー内に窒素フロー有り
<ASTM試験片の射出成形条件>
射出成形機:品番 EC40、東芝機械(株)製
シリンダー温度:230℃
金型温度:40℃
<線膨張係数測定用角板の射出成形条件>
射出成形機:品番 AUTOSHOT Tseries MODEL100D、FANUC社製
シリンダー温度:230℃
金型温度:40℃
試験片:角板(100mm×100mm×2mm)
[比較例1]
(固体状チタン触媒成分(β1)の調製)
無水塩化マグネシウム75g、デカン280.3gおよび2-エチルヘキシルアルコール308.3gを130℃で3時間加熱反応させて均一溶液とした後、この溶液中にエチルベンゾエート17.7gを添加し、さらに130℃にて1時間攪拌混合を行った。
窒素で置換した内容積2リットルの攪拌機付きの三つ口フラスコに、上記の固体状チタン触媒成分(β1)120グラム(60.1ミリモル-Ti)を含むヘプタンスラリーを投入し、さらに、脱水したヘプタンを加えて、全量を1リットルとした。これを20℃以下に制御しながら攪拌し、トリエチルアルミニウム180ミリモルを加えた。20℃のまま、120分間プロピレンを所定量吸収させ、残留プロピレンを窒素で置換して、ヘプタンを用いて充分洗浄を行い、予備重合触媒成分を1.3kg得た(10g-PP/g-固体状チタン触媒成分)。
内容量58Lの環状重合器にプロピレンを43kg/hr、水素を140NL/hr、触媒スラリーを固体触媒成分として0.87g/hr、トリエチルアルミニウム2.94mL/hr、ジシクロペンチルジメトキシシラン3.2mL/hrを連続的に供給し、気相の存在しない満液の状態にて重合した。環状反応器の温度は70℃であり、圧力は3.5MPa/Gであった。
プロピレン系ブロック共重合体(A‘-1)は、実施例1と同様に成形した。成形品の物性および射出成形品外観、射出成形流動性の評価結果を表1に示す。
(固体状チタン触媒成分(β2)の調製)
無水塩化マグネシウム75g、デカン280.3gおよび2-エチルヘキシルアルコール308.3gを130℃で3時間加熱反応させて均一溶液とした後、この溶液中に無水フタル酸17.5gを添加し、さらに130℃にて1時間攪拌混合を行った。
窒素で置換した内容積2リットルの攪拌機付きの三つ口フラスコに、上記の固体状チタン触媒成分120グラム(65.1ミリモル-Ti)を含むヘプタンスラリーを投入し、さらに、脱水したヘプタンを加えて、全量を1リットルとした。これを20℃以下に制御しながら攪拌し、トリエチルアルミニウム195ミリモルを加えた。20℃のまま、120分間プロピレンを所定量吸収させ、残留プロピレンを窒素で置換して、ヘプタンを用いて充分洗浄を行い、予備重合触媒成分を1.3kg得た(10g-PP/g-固体状チタン触媒成分)。
内容量58Lの環状重合器にプロピレンを42kg/hr、水素を135NL/hr、触媒スラリーを固体触媒成分として0.99g/hr、トリエチルアルミニウム3.87mL/hr、ジシクロペンチルジメトキシシラン4.05mL/hrを連続的に供給し、気相の存在しない満液の状態にて重合した。環状反応器の温度は70℃であり、圧力は3.5MPa/Gであった。
プロピレン系ブロック共重合体(A‘-2)は、実施例1と同様に成形した。成形品の物性および射出成形品外観、射出成形流動性の評価結果を表1に示す。フローマーク評価に用いた射出成形体の写真を図3に示す。
固体状チタン触媒成分(α1)を用いて、気相重合器の重合条件で滞留時間を0.47時間にした以外は実施例1と同様に重合を行い、プロピレン系ブロック共重合体(A-2)を得た。なお、室温n-デカン可溶な部分(Dsol)は8.6重量%であり、室温n-デカン不溶な部分(Dinsol)は91.4重量%であった。
プロピレン系ブロック共重合体(A-2)は、実施例1と同様にASTM試験片を成形した。成形品の物性および射出成形品外観、射出成形流動性の評価結果を表2に示す。
固体状チタン触媒成分(β1)を用いて、気相重合器の重合条件で滞留時間を0.37時間にした以外は比較例1と同様に重合を行い、プロピレン系ブロック共重合体(A‘-3)を得た。
プロピレン系ブロック共重合体(A‘-3)は、実施例1と同様にASTM試験片を成形した。成形品の物性および射出成形品外観、射出成形流動性の評価結果を表2に示す。
固体状チタン触媒成分(β2)を用いて、気相重合器の重合条件で滞留時間を0.41時間にした以外は比較例2と同様に重合を行い、プロピレン系ブロック共重合体(A‘-4)を得た。
プロピレン系ブロック共重合体(A‘-4)は、実施例1と同様にASTM試験片を成形した。成形品の物性および射出成形品外観、射出成形流動性の評価結果を表2に示す。
固体状チタン触媒成分(α1)を用いて、気相重合器の重合条件で滞留時間を0.32時間にした以外は実施例1と同様に重合を行い、プロピレン系ブロック共重合体(A-3)を得た。なお、室温n-デカン可溶な部分(Dsol)は5.9重量%であり、室温n-デカン不溶な部分(Dinsol)は94.1重量%であった。
プロピレン系ブロック共重合体(A-3)は、実施例1と同様にASTM試験片を成形した。成形品の物性および射出成形品外観、射出成形流動性の評価結果を表3に示す。
固体状チタン触媒成分(β1)を用いて、気相重合器の重合条件で滞留時間を0.26時間にした以外は比較例1と同様に重合を行い、プロピレン系ブロック共重合体(A‘-5)を得た。
プロピレン系ブロック共重合体(A‘-5)は、実施例1と同様にASTM試験片を成形した。成形品の物性および射出成形品外観、射出成形流動性の評価結果を表3に示す。
固体状チタン触媒成分(β2)を用いて、気相重合器の重合条件で滞留時間を0.28時間にした以外は比較例2と同様に重合を行い、プロピレン系ブロック共重合体(A‘-6)を得た。
プロピレン系ブロック共重合体(A‘-6)は、実施例1と同様にASTM試験片を成形した。成形品の物性および射出成形品外観、射出成形流動性の評価結果を表3に示す。
実施例1で製造されたプロピレン系ブロック共重合体(A-1)100重量部に対して、結晶核剤アデカスタブNA21(旭電化(株)商標)0.3重量部、耐熱安定剤IRGANOX1010(チバガイギー(株)商標)0.1重量部、耐熱安定剤IRGAFOS168(チバガイギー(株)商標)0.1重量部、耐熱安定剤IRGANOX1076(チバガイギー(株)商標)0.1重量部、ステアリン酸カルシウム0.1重量部をタンブラーにて混合後、実施例1と同様に二軸押出機にて溶融混練してペレット状のポリプロピレン樹脂組成物を調製、実施例1と同様に射出成形機にて試験片を作成した。成形品の機械物性および外観を表4に示す。
実施例4において、プロピレン系ブロック共重合体(A-1)100重量部の代わりに、比較例1で製造されたプロピレン系ブロック共重合体(A‘-1)100重量部を用いた以外は、実施例4と同様に試験片を作成した。成形品の機械物性および外観を表4に示す。
実施例4において、プロピレン系ブロック共重合体(A-1)100重量部の代わりに、比較例2で製造されたプロピレン系ブロック共重合体(A‘-2)100重量部を用いた以外は、実施例4と同様に試験片を作成した。成形品の機械物性および外観を表4に示す。
実施例1で製造されたプロピレン系ブロック共重合体(A-1)60重量部、エチレン-ブテン共重合体ゴム(タフマーA1050(三井化学(株)商標)20重量部、タルク(ホワイトフィラー5000PJ(商標)、松村産業(株)製)20量部、耐熱安定剤IRGANOX1010(チバガイギー(株)商標)0.1重量部、耐熱安定剤IRGAFOS168(チバガイギー(株)商標)0.1重量部、耐熱安定剤IRGANOX1076(チバガイギー(株)商標)0.1重量部、ステアリン酸カルシウム0.1重量部をタンブラーにて混合後、実施例1と同様に二軸押出機にて溶融混練してペレット状のポリプロピレン樹脂組成物を調製、実施例1と同様に射出成形機にて試験片(ASTM試験片、線膨張係数測定用角板)を作成した。成形品の機械物性および外観を表5に示す。
実施例5において、プロピレン系ブロック共重合体(A-1)60重量部の代わりに、比較例1で製造されたプロピレン系ブロック共重合体(A‘-1)60重量部を用いた以外は、実施例5と同様に試験片を作成した。成形品の機械物性および外観を表5に示す。
実施例5において、プロピレン系ブロック共重合体(A-1)60重量部の代わりに、比較例2で製造されたプロピレン系ブロック共重合体(A‘-2)60重量部を用いた以外は、実施例5と同様に試験片を作成した。成形品の機械物性および外観を表5に示す。
(固体状チタン触媒成分(α2)の調製)
内容積2リットルの高速撹拌装置(特殊機化工業製(TKホモミクサーM型))を充分窒素置換した後、この装置に精製デカン700ml、市販塩化マグネシウム10g、エタノール24.2gおよび商品名レオドールSP-S20(花王(株)製ソルビタンジステアレート)3gを入れ、この懸濁液を撹拌しながら系を昇温し、懸濁液を120℃にて800rpmで30分撹拌した。次いでこの懸濁液を、沈殿物が生じないように高速撹拌しながら、内径5mmのテフロン(登録商標)製チューブを用いて、予め-10℃に冷却された精製デカン1リットルを張り込んである2リットルのガラスフラスコ(攪拌機付)に移した。移液により生成した固体を濾過し、精製n-ヘプタンで充分洗浄することにより、塩化マグネシウム1モルに対してエタノールが2.8モル配位した固体状付加物を得た。この固体状付加物をデカンで懸濁状にして、マグネシウム原子に換算して23ミリモルの上記固体状付加物を、-20℃に保持した四塩化チタン100ml中に、攪拌下、導入して混合液を得た。この混合液を5時間かけて80℃に昇温し、80℃に達したところで、3,6-ジメチルシクロヘキサン-1,2-ジカルボン酸ジイソブチル(シス体、トランス体混合物)を、固体状付加物のマグネシウム原子1モルに対して0.085モルの割合の量で添加し、40分間で110℃まで昇温した。110℃に到達したところで更にシクロヘキサン1,2-ジカルボン酸ジイソブチル(シス体、トランス体混合物)を固体状付加物のマグネシウム原子1モルに対して0.0625モルの割合の量で添加し、温度を110℃で90分間攪拌しながら保持することによりこれらを反応させた。
次に窒素で置換した内容積200ミリリットルの攪拌機付きの三つ口フラスコに、脱水したヘキサンを加え、トリエチルアルミニウム0.75ミリモル、さらに上記の固体状チタン触媒成分(α2)の懸濁液をチタン原子換算で0.25ミリモル投入、全量を50ミリリットルとした。これを攪拌下、20℃を維持して60分間プロピレンを所定量吸収させた。その後、残留プロピレンを窒素で置換して、ヘキサンを用いて充分洗浄を行い、予備重合触媒成分を得た(3g-PP/g-固体状チタン触媒成分)。
内容積2リットルの重合器に、室温で500gのプロピレンおよび水素6NLを加えた後、トリエチルアルミニウムを0.75ミリモル、シクロヘキシルメチルジメトキシシランを0.025ミリモル、および固体状チタン触媒成分(α2)をチタン原子換算で0.0054ミリモル加え、速やかに重合器内を70℃まで昇温した。70℃で20分重合した後、降温させながらプロピレンをパージした。その後窒素置換を数回繰り返した。そして、水素0.04NLを加えた後、エチレン/(エチレン+プロピレン)=43モル%の混合ガスを用いて全圧0.4MPaとして、気相下で共重合を行った。ゴム量(Dsol)が約18%に達するまで重合した。反応終了後、少量のメタノールにて反応停止し、プロピレンをパージした。更に得られた重合体粒子を室温で一晩、減圧乾燥してプロピレン系ブロック共重合体(A-4)を得た。なお、室温n-デカン可溶な部分(Dsol)は18.4重量%であり、室温n-デカン不溶な部分(Dinsol)は81.6重量%であった。
プロピレン系ブロック共重合体(A-4)100重量部、耐熱安定剤IRGANOX1010(チバジャパン(株)商標)0.1重量部、耐熱安定剤IRGAFOS168(チバジャパン(株)商標)0.1重量部、耐熱安定剤IRGANOX1076(チバジャパン(株)商標)0.1重量部およびステアリン酸カルシウム0.1重量部をブレンド後、単軸押出機にて下記条件で溶融混練してペレット化した。得られたペレットを射出成形機[品番 EC40、東芝機械(株)製]にて下記条件でJIS小型試験片および小型角板を成形した。
単軸混練機 : 品番 ラボプラストミル10M100、東洋精機(株)製
混練温度 : 210℃
スクリュー回転数 : 60rpm
ホッパー内に窒素フロー有り
<射出成形条件>
射出成形機:品番 EC40、東芝機械(株)製
シリンダー温度:190℃
金型温度:40℃
JIS小型試験片と小型角板はファミリーモールドにて成形
[実施例7]
(本重合)
固体状チタン触媒成分(α2)を用い、気相下で共重合時間をゴム量(Dsol)が約25%に達するまで重合時間を延長した以外は、実施例6と同様に行った。得られた重合体粒子を室温で一晩、減圧乾燥してプロピレン系ブロック共重合体(A-5)を得た。なお、室温n-デカン可溶な部分(Dsol)は24.1重量%であり、室温n-デカン不溶な部分(Dinsol)は75.9重量%であった。
プロピレン系ブロック共重合体(A-5)は実施例6と同様にブレンド、造粒、射出成形を行った。成形品の物性を表6に示す。
(本重合)
固体状チタン触媒成分(α2)を用い、気相下での水素添加をしなかった以外は、実施例6と同様に行った。得られた重合体粒子を室温で一晩、減圧乾燥してプロピレン系ブロック共重合体(A-6)を得た。なお、室温n-デカン可溶な部分(Dsol)は17.6重量%であり、室温n-デカン不溶な部分(Dinsol)は82.4重量%であった。
プロピレン系ブロック共重合体(A-6)は実施例6と同様にブレンド、造粒、射出成形を行った。成形品の物性を表6に示す。
(固体状チタン触媒成分(β3)の調製)
内容積2リットルの高速撹拌装置(特殊機化工業製(TKホモミクサーM型))を充分窒素置換した後、この装置に精製デカン700ml、市販塩化マグネシウム10g、エタノール24.2gおよび商品名レオドールSP-S20(花王(株)製ソルビタンジステアレート)3gを入れ、この懸濁液を撹拌しながら系を昇温し、懸濁液を120℃にて800rpmで30分撹拌した。次いでこの懸濁液を、沈殿物が生じないように高速撹拌しながら、内径5mmのテフロン(登録商標)製チューブを用いて、予め-10℃に冷却された精製デカン1リットルを張り込んである2リットルのガラスフラスコ(攪拌機付)に移した。移液により生成した固体を濾過し、精製n-ヘプタンで充分洗浄することにより、塩化マグネシウム1モルに対してエタノールが2.8モル配位した固体状付加物を得た。この固体状付加物をデカンで懸濁状にして、マグネシウム原子に換算して23ミリモルの上記固体状付加物を、-20℃に保持した四塩化チタン100ml中に、攪拌下、導入して混合液を得た。この混合液を5時間かけて80℃に昇温し、80℃に達したところで、フタル酸ジイソブチルを、固体状付加物のマグネシウム原子1モルに対して0.15モルの割合の量で添加し、40分間で120℃まで昇温した。温度を120℃で90分間攪拌しながら保持することによりこれらを反応させた。
次に窒素で置換した内容積200ミリリットルの攪拌機付きの三つ口フラスコに、脱水したヘキサンを加え、トリエチルアルミニウム0.75ミリモル、さらに上記の固体状チタン触媒成分(β3)の懸濁液をチタン原子換算で0.25ミリモル投入、全量を50ミリリットルとした。これを攪拌下、20℃を維持して60分間プロピレンを所定量吸収させた。その後、残留プロピレンを窒素で置換して、ヘキサンを用いて充分洗浄を行い、予備重合触媒成分を得た(3g-PP/g-固体状チタン触媒成分)。
内容積2リットルの重合器に、室温で500gのプロピレンおよび水素5.3NLを加えた後、トリエチルアルミニウムを0.84ミリモル、シクロヘキシルメチルジメトキシシランを0.028ミリモル、および固体状チタン触媒成分(β3)をチタン原子換算で0.0054ミリモル加え、速やかに重合器内を70℃まで昇温した。70℃で20分重合した後、降温させながらプロピレンをパージした。その後、窒素置換を数回繰り返した。そして、水素0.04NLを加えた後、エチレン/(エチレン+プロピレン)=43モル%の混合ガスを用いて全圧0.4MPaとして、気相下で共重合を行った。ゴム量(Dsol)が約18重量%に達するまで重合した。反応終了後、少量のメタノールにて反応停止し、プロピレンをパージした。更に得られた重合体粒子を室温で一晩、減圧乾燥してプロピレン系ブロック共重合体(A‘-7)を得た。
プロピレン系ブロック共重合体(A‘-7)は実施例6と同様にブレンド、造粒、射出成形を行った。成形品の物性を表6に示す。
(本重合)
固体状チタン触媒成分(β3)を用い、気相下での水素添加をしなかった以外は、実施例6と同様に行った。得られた重合体粒子を室温で一晩、減圧乾燥してプロピレン系ブロック共重合体(A‘-8)を得た。
(成形)
プロピレン系ブロック共重合体(A‘-8)は実施例6と同様に、ブレンド、造粒、射出成形を行った。成形品の物性を表6に示す。
Claims (13)
- 室温n-デカンに可溶な部分(Dsol)5~80重量%と室温n-デカンに不溶な部分(Dinsol)20~95重量%から構成され(ただし、DsolとDinsolの合計量は100重量%である)、
以下の要件[1]~[3]を同時に満たすことを特徴とするプロピレン系ブロック共重合体。
[1]Dsolの分子量分布(Mw/Mn)が7.0以上、30以下、
[2]Dinsolの分子量分布(Mw/Mn)が7.0以上、30以下、かつMz/Mwが6.0以上、20以下、
[3]Dinsolのペンタド分率(mmmm)が93%以上。 - 以下の要件[4]をさらに満たすことを特徴とする請求項1に記載のプロピレン系ブロック共重合体。
[4]Dsolの極限粘度[η](dl/g)が、1.5以上、10.0以下。 - 以下の要件[5]をさらに満たすことを特徴とする請求項1または2に記載のプロピレン系ブロック共重合体。
[5]DinsolのMz/Mnが70以上、300以下。 - 室温n-デカンに可溶な部分(Dsol)は、プロピレンと、エチレンおよび炭素原子数4~20のα-オレフィンから選ばれる一種以上のオレフィンとからなる共重合体ゴムが主成分であり、
室温n-デカンに不溶な部分(Dinsol)は、プロピレン98.5~100mol%と、エチレンおよび炭素原子数4~20のα-オレフィンから選ばれる一種以上のオレフィン0~1.5mol%とからなる結晶性プロピレン系(共)重合体が主成分であることを特徴とする請求項1~3のいずれか1項に記載のプロピレン系ブロック共重合体。 - 前記共重合体ゴムを製造する工程が、プロピレンと、エチレンおよび炭素原子数4~20のα-オレフィンから選ばれる一種以上のオレフィンとを1段階で重合することを特徴とする請求項4に記載のプロピレン系ブロック共重合体。
- チタン、マグネシウム、ハロゲンおよび下記式(1)で特定される環状エステル化合物(a)と下記式(2)で特定される環状エステル化合物(b)を含む固体状チタン触媒成分(I)と、
周期表の第1族、第2族および第13族から選ばれる金属原子を含む有機金属化合物(II)と、
必要に応じて電子供与体(III)と、
を含むオレフィン重合用触媒の存在下にプロピレンを含有するオレフィンを重合して得られたものであることを特徴とする請求項1~5のいずれか1項に記載のプロピレン系ブロック共重合体。
R2およびR3はそれぞれ独立にCOOR1またはRであり、R2およびR3のうち少なくとも1つはCOOR1である。環状骨格中の単結合(C-Cb結合、R3がCOOR1である場合のCa-Cb結合、およびC-C結合(nが6~10の場合))は、二重結合に置き換えられていてもよい。
R1は、それぞれ独立に炭素原子数1~20の1価の炭化水素基である。
複数個あるRは、それぞれ独立に水素原子、炭素原子数1~20の炭化水素基、ハロゲン原子、窒素含有基、酸素含有基、リン含有基、ハロゲン含有基およびケイ素含有基から選ばれる原子または基であり、互いに結合して環を形成していてもよいが、少なくとも1つのRは水素原子ではない。
Rが互いに結合して形成される環の骨格中に、二重結合が含まれていてもよく、該環の骨格中に、COOR1が結合したCaを2つ以上含む場合は、該環の骨格をなす炭素原子の数は5~10である。
R4およびR5はそれぞれ独立にCOOR1または水素原子であり、R4およびR5のうち少なくとも1つはCOOR1である。R1は、それぞれ独立に炭素原子数1~20の1価の炭化水素基である。環状骨格中の単結合(C-Cb結合、R5がCOOR1である場合のCa-Cb結合、およびC-C結合(nが6~10の場合))は、二重結合に置き換えられていてもよい。 - 前記式(1)および/または(2)において、前記環状骨格中の炭素原子間結合のすべてが単結合であることを特徴とする請求項6に記載のプロピレン系ブロック共重合体。
- 前記式(1)および/または(2)において、n=6であることを特徴とする請求項6に記載のプロピレン系ブロック共重合体。
- 前記環状エステル化合物(a)が下記式(1a)であり、前記環状エステル化合物(b)が下記式(2a)であることを特徴とする請求項6に記載のプロピレン系ブロック共重合体。
環状骨格中の単結合(C-C結合(nが6~10の場合)、Ca-C結合およびCb-C結合)は、二重結合に置き換えられていてもよい。
R1は、それぞれ独立に炭素原子数1~20の1価の炭化水素基である。
複数個あるRは、それぞれ独立に水素原子または炭素原子数1~20の炭化水素基、ハロゲン原子、窒素含有基、酸素含有基、リン含有基、ハロゲン含有基およびケイ素含有基から選ばれる原子または基であり、互いに結合して環を形成していてもよいが、少なくとも1つのRは水素原子ではない。
Rが互いに結合して形成される環の骨格中に二重結合が含まれていてもよく、該環の骨格中に、COOR1が結合したCaを2つ以上含む場合は、該環の骨格をなす炭素原子の数は5~10である。
R1は、それぞれ独立に炭素原子数1~20の1価の炭化水素基である。環状骨格中の単結合(C-C結合(nが6~10の場合)、Ca-C結合およびCb-C結合)は、二重結合に置き換えられていてもよい。 - 前記式(1a)および(2a)において、前記環状骨格中の炭素原子間結合のすべてが単結合であることを特徴とする請求項9に記載のプロピレン系ブロック共重合体。
- 前記式(1a)および(2a)において、n=6であることを特徴とする請求項9に記載のプロピレン系ブロック共重合体。
- 請求項1~11のいずれか一項に記載のプロピレン系ブロック共重合体と、無機充填剤および/またはエラストマーを含んでなるプロピレン樹脂組成物。
- 請求項1~11のいずれか一項に記載のプロピレン系ブロック共重合体を含んでなる成形体。
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US13/120,031 US8729189B2 (en) | 2008-09-22 | 2009-09-17 | Propylene-based block copolymer, composition containing the copolymer, and molded products obtained therefrom |
JP2010529792A JP5441909B2 (ja) | 2008-09-22 | 2009-09-17 | プロピレン系ブロック共重合体、該共重合体を含む組成物およびこれらから得られる成形体 |
EP09814637.6A EP2330139B1 (en) | 2008-09-22 | 2009-09-17 | Propylene-based block copolymer and composition containing said copolymer, and molded body obtained therefrom |
BRPI0919007-4A BRPI0919007B1 (pt) | 2008-09-22 | 2009-09-17 | Copolímero em bloco à base de propileno, composição quecontém o copolímero e produtos moldados obtidos a partirdeste |
CN200980136201.1A CN102159608B (zh) | 2008-09-22 | 2009-09-17 | 丙烯系嵌段共聚物、包含该共聚物的组合物及由它们得到的成型体 |
KR1020117008122A KR101284938B1 (ko) | 2008-09-22 | 2009-09-17 | 프로필렌계 블록 공중합체, 이 공중합체를 포함하는 조성물 및 이들로부터 얻어지는 성형체 |
ES09814637.6T ES2445100T3 (es) | 2008-09-22 | 2009-09-17 | Copolímero en bloque a base de propileno y composición que contiene dicho copolímero, y cuerpo moldeado obtenido del mismo |
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JP5441909B2 (ja) | 2014-03-12 |
US8729189B2 (en) | 2014-05-20 |
CN102159608B (zh) | 2014-05-21 |
ES2445100T3 (es) | 2014-02-28 |
RU2463313C1 (ru) | 2012-10-10 |
EP2330139A4 (en) | 2012-07-25 |
KR20110058877A (ko) | 2011-06-01 |
KR101284938B1 (ko) | 2013-07-10 |
BRPI0919007B1 (pt) | 2019-04-24 |
BRPI0919007A2 (pt) | 2015-12-08 |
US20110172353A1 (en) | 2011-07-14 |
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