JP3715670B2 - Process for producing olefin polymer composition - Google Patents

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an olefin polymer composition.Manufacturing methodMore particularly, the olefin polymer composition having excellent mechanical strength and impact resistance strength.Manufacturing methodIt is about.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
Conventionally, crystalline polypropylene is generally known as a polymer excellent in rigidity, heat resistance, surface glossiness, and the like. A propylene block copolymer having both a polypropylene component and a rubber component is also known as a propylene polymer having improved impact resistance over crystalline polypropylene.
[0003]
Such a propylene polymer has features such as low specific gravity and easy recycling, and thus has attracted attention in terms of environmental protection, and is desired to be used in a wider range of applications.
[0004]
For this reason, propylene polymers, particularly crystalline polypropylene, are further desired to have improved impact resistance.
Conventionally, as a method for improving the impact resistance of a propylene polymer, a method of forming a propylene block copolymer as described above, or a modifier such as polyethylene or rubber-like substance is blended with crystalline polypropylene. Methods for forming polypropylene compositions are known. As such a rubbery substance, amorphous or low crystalline ethylene / propylene random copolymer (EPR), polyisobutylene, polybutadiene and the like are generally used.
[0005]
However, in order to improve impact resistance by adding the rubbery material as described above, it is necessary to contain a large amount of the rubbery material in polypropylene. However, a polypropylene composition containing a large amount of the rubbery material is Although impact properties are improved, mechanical strength such as rigidity, heat resistance and surface hardness are greatly reduced.
[0006]
For this reason, a polypropylene composition containing an inorganic filler such as talc in order to impart rigidity together with the rubbery material as described above has been proposed.
However, the polypropylene composition containing a large amount of rubber-like substance has a problem in that it cannot be used for applications requiring high rigidity because there is a limit in improving the rigidity by blending inorganic fillers such as talc. .
[0007]
Moreover, the propylene polymer obtained by a prior art is not necessarily sufficient in rigidity and heat resistance depending on the use, and its use may be limited.
For this reason, the appearance of a polypropylene-based olefin polymer composition having excellent mechanical strength such as rigidity, moldability, heat resistance and excellent impact strength is desired.
[0008]
OBJECT OF THE INVENTION
The present invention has been made in view of the prior art as described above, and is an olefin polymer composition excellent in moldability, heat resistance, rigidity, and impact strength.Manufacturing methodThe purpose is to provide.
[0009]
SUMMARY OF THE INVENTION
  The method for producing an olefin polymer composition according to the present invention comprises:
[I] (A) Solid titanium catalyst component containing magnesium, titanium, halogen and polyvalent carboxylic acid ester,
      (B) an organometallic compound, and
      (C)1 , An electron donor comprising at least one selected from 3-diethers; Or the following formula ( ii And at least one selected from dimethoxy compounds represented by , 3 An electron donor comprising at least one selected from diethers
[Chemical 2]
(Wherein R^aAnd R^cEach independently represents a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or a carbon adjacent to Si is a secondary carbon or a tertiary carbon. A certain hydrocarbon group is shown. )
In the presence of an olefin polymerization catalyst (1) consisting of
  [I-1] a step of producing a crystalline polypropylene component by homopolymerizing propylene or copolymerizing propylene and another α-olefin;
  [I-2] A step of producing a low-crystalline or non-crystalline ethylene / propylene copolymer component by copolymerizing ethylene and propylene in any order to produce a propylene-based block copolymer With manufacturing,
[II] (D) a transition metal compound containing a ligand having a cyclopentadienyl skeleton,
  and
(E) (E-1) Organoaluminum oxy compound
      (E-2) Lewis acid or ionic compound
  In the presence of an olefin polymerization catalyst (2) consisting of
  Ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized to produce a low crystalline or non-crystalline ethylene copolymer,
  Next, the propylene block copolymer and the low crystalline or non-crystalline ethylene copolymer are kneaded, and 30 to 98 parts by weight of the propylene block copolymer, and the low crystalline or It is characterized by producing a composition comprising 70 to 2 parts by weight of an amorphous ethylene copolymer.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the olefin polymer composition according to the present invention.Manufacturing methodWill be described in detail.
In the present invention, the term “polymerization” may be used to mean not only homopolymerization but also copolymerization, and the term “polymer” refers not only to homopolymers but also to copolymers. May also be used to encompass.
[0011]
The olefin polymer composition according to the present invention is:
[I] a propylene-based block copolymer produced using a specific olefin polymerization catalyst (1),
[II] An ethylene copolymer produced by using a specific olefin polymerization catalyst (2).
[0012]
The components [I] and [II] forming the olefin polymer composition according to the present invention will be specifically described.
[I] Propylene block copolymer
The propylene-based block copolymer [I] forming the olefin polymer composition according to the present invention is:
(A) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor,
(B) an organometallic compound, and as required
(C) In the presence of an olefin polymerization catalyst (1) comprising an electron donor,
[I-1] a step of producing a crystalline polypropylene component by homopolymerizing propylene or copolymerizing propylene and another α-olefin;
[I-2] The step of producing a low crystalline or non-crystalline ethylene / propylene copolymer component by copolymerizing ethylene and propylene can be obtained in any order.
[0013]
First, each catalyst component forming the olefin polymerization catalyst used when producing the propylene-based block copolymer [I] will be described.
(A) Solid titanium catalyst component
The (A) solid titanium catalyst component used in the present invention can be prepared by contacting a magnesium compound, a titanium compound and an electron donor as described below.
[0014]
(A) Specific examples of the titanium compound used for the preparation of the solid titanium catalyst component include a tetravalent titanium compound represented by the following formula.
Ti (OR)_gX_4-g
(In the formula, R is a hydrocarbon group, X is a halogen atom, and g is 0 ≦ g ≦ 4)
As such a titanium compound, specifically,
TiCl_Four, TiBr_Four, TiI_FourTitanium tetrahalides such as;
Ti (OCH_Three) Cl_Three, Ti (OC₂H_Five) Cl_Three, Ti (O-n-C_FourH₉) Cl_Three, Ti (OC₂H_FiveBr_Three, Ti (O-iso-C_FourH₉Br_ThreeTrihalogenated alkoxy titaniums such as;
Ti (OCH_Three)₂Cl₂, Ti (OC₂H_Five)₂Cl₂, Ti (O-n-C_FourH₉)₂Cl₂, Ti (OC₂H_Five)₂Br₂Dihalogenated dialkoxytitanium such as;
Ti (OCH_Three)_ThreeCl, Ti (OC₂H_Five)_ThreeCl, Ti (O-n-C_FourH₉)_ThreeCl, Ti (OC₂H_Five)_ThreeMonohalogenated trialkoxytitanium such as Br;
Ti (OCH_Three)_Four, Ti (OC₂H_Five)_Four, Ti (O-n-C_FourH₉)_Four, Ti (O-iso-C_FourH₉)_Four, Ti (O-2-ethylhexyl)_FourExamples thereof include tetraalkoxytitanium.
[0015]
Among these, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.
[0016]
Examples of the magnesium compound used for the preparation of the solid titanium catalyst component (A) include a magnesium compound having reducibility and a magnesium compound having no reducibility.
[0017]
Here, examples of the magnesium compound having reducibility include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such reducing magnesium compounds include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl Examples include magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium hydride, and the like. These magnesium compounds may be used alone or may form a complex compound with an organometallic compound described later. Further, these magnesium compounds may be liquid, solid, or may be derived by reacting metallic magnesium with a corresponding compound. It can also be derived from magnesium metal using the above method during catalyst preparation.
[0018]
Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy chloride Alkoxymagnesium halides such as magnesium and octoxymagnesium chloride; Allyloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium Alkoxymagnesium; allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium And carboxylic acid salts of magnesium such as magnesium laurate and magnesium stearate.
[0019]
These non-reducing magnesium compounds may be compounds derived from the above-described reducing magnesium compounds or compounds derived during the preparation of the catalyst component.
[0020]
In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, the reducing magnesium compound is converted to a halogen compound such as a halogen, a halogen-containing organosilicon compound or a halogen-containing aluminum compound, an alcohol or an ester. And a compound having an active carbon-oxygen bond, such as a ketone or an aldehyde, or a polysiloxane compound.
[0021]
In the present invention, in addition to the magnesium compound having the reducing property and the magnesium compound not having the reducing property, the magnesium compound may be a complex compound, a double compound or another metal compound of the magnesium compound and another metal. It may be a mixture. Furthermore, two or more of the above compounds may be used in combination.
[0022]
As the magnesium compound used for the preparation of the solid titanium catalyst component (A), many magnesium compounds can be used in addition to those described above. In the finally obtained solid titanium catalyst component (A), halogen-containing compounds can be used. It is preferable to take the form of a magnesium compound. Therefore, when a magnesium compound containing no halogen is used, it is preferable to cause a contact reaction with a halogen-containing compound during the preparation.
[0023]
Among the magnesium compounds described above, magnesium compounds having no reducing property are preferable, halogen-containing magnesium compounds are more preferable, and magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are particularly preferable.
[0024]
The solid titanium catalyst component (A) used in the present invention is formed by bringing the magnesium compound as described above into contact with the titanium compound and the electron donor (a) as described above.
[0025]
Examples of the electron donor (a) used in preparing the solid titanium catalyst component (A) include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic acids or inorganic acids, and ethers. , Acid amide, acid anhydride, ammonia, amine, nitrile, isocyanate, nitrogen-containing cyclic compound, oxygen-containing cyclic compound and the like. More specifically,
1 carbon atom such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol ~ 18 alcohols,
C1-C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol, trichlorohexanol,
Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol,
Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone,
Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde,
Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, cyclohexanecarboxyl Ethyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate C2-C30 organic acid esters such as ethyl, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate,
C2-15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride,
Ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether,
Acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide,
Amines such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylenediamine, hexamethylenediamine,
Nitriles such as acetonitrile, benzonitrile, trinitrile,
Acid anhydrides such as acetic anhydride, phthalic anhydride, benzoic anhydride,
Pyrroles such as pyrrole, methyl pyrrole and dimethyl pyrrole
Pyrroline; pyrrolidine; indole; pyridines such as pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, pyridine chloride,
Nitrogen-containing cyclic compounds such as piperidines, quinolines, isoquinolines,
Examples thereof include cyclic oxygenates such as tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolefuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, and ditedropyran.
[0026]
Moreover, as an organic acid ester, the polyvalent carboxylic acid ester which has the frame | skeleton shown by the following general formula can be mentioned as a particularly preferable example.
[0027]
[Chemical 1]
[0028]
In the above formula, R¹Is a substituted or unsubstituted hydrocarbon group, R², R^Five, R⁶Is hydrogen or a substituted or unsubstituted hydrocarbon group, R^Three, R^FourIs hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. Also R^ThreeAnd R^FourAnd may be connected to each other to form a ring structure. Hydrocarbon group R¹~ R⁶In the case where is substituted, the substituent includes a heteroatom such as N, O, S, etc., for example, C—O—C, COOR, COOH, OH, SO_ThreeH, -C-N-C-, NH₂It has groups such as.
[0029]
As such a polyvalent carboxylic acid ester, specifically,
Diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate, diethyl isopropylmalonate, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, dibutyl Diethyl malonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, Aliphatic polycarboxylic acid esters such as dioctyl citraconic acid,
Alicyclic polycarboxylic acid esters such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid,
Monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, phthalate Di-n-heptyl acrylate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, trimellit Aromatic polycarboxylic acid esters such as triethyl acid and dibutyl trimellitic acid,
Examples include heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.
[0030]
Other examples of polycarboxylic acid esters include long-chain dicarboxylic acids such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Examples include esters of acids.
[0031]
In the present invention, as the electron donor (a), an organosilicon compound (c-i) or a polyether compound (c-ii) described later can be used as the electron donor (C).
[0032]
In addition to these, water, anionic, cationic, and nonionic surfactants can also be used.
In the present invention, as the electron donor (a), among these, carboxylic acid esters are preferable, and polyvalent carboxylic acid esters, particularly phthalic acid esters are particularly preferable.
[0033]
Two or more of these compounds can be used in combination.
Further, when the titanium compound, the magnesium compound and the electron donor as described above are brought into contact with each other, a carrier-supporting solid titanium catalyst component (A) can be prepared using the following particulate carrier.
[0034]
Such carriers include Al.₂O_Three, SiO₂, B₂O_Three, MgO, CaO, TiO₂, ZnO, Zn₂O, SnO₂, BaO, ThO and resins such as styrene-divinylbenzene copolymer. Of these, preferably SiO₂, Al₂O_ThreeMgO, ZnO, Zn₂O etc. can be mentioned.
[0035]
In addition, you may make said component contact in presence of other reaction reagents, such as a silicon, phosphorus, and aluminum, for example.
The solid titanium catalyst component (A) can be produced by bringing a titanium compound, a magnesium compound and an electron donor as described above into contact with each other, and can be produced by any method including a known method.
[0036]
Several specific methods for producing these solid titanium catalyst components (A) will be briefly described below.
(1) A method in which a solution comprising a magnesium compound, an electron donor, and a hydrocarbon solvent is contacted with an organometallic compound to precipitate a solid, or contacted with a titanium compound while being precipitated.
[0037]
(2) A method in which a complex composed of a magnesium compound and an electron donor is contacted with and reacted with an organometallic compound, and then a titanium compound is contacted and reacted.
(3) A method in which a titanium compound and preferably an electron donor are contacted with a contact product of an inorganic carrier and an organic magnesium compound. At this time, the contact product may be previously contacted with a halogen-containing compound and / or an organometallic compound.
[0038]
(4) A method of obtaining an inorganic or organic carrier carrying a magnesium compound from a mixture of a magnesium compound, an electron donor, optionally further containing a hydrocarbon solvent, and an inorganic or organic carrier, and then contacting the titanium compound .
[0039]
(5) A method of obtaining a solid titanium catalyst component on which magnesium or titanium is supported by contacting a solution containing a magnesium compound, a titanium compound, an electron donor, and optionally a hydrocarbon solvent, with an inorganic or organic carrier.
[0040]
(6) A method in which a liquid organic magnesium compound is contacted with a halogen-containing titanium compound. At this time, the electron donor is used once.
(7) A method in which a liquid organic organomagnesium compound is contacted with a halogen-containing compound and then contacted with a titanium compound. At this time, the electron donor is used once.
[0041]
(8) A method in which an alkoxy group-containing magnesium compound is contacted with a halogen-containing titanium compound. At this time, the electron donor is used once.
(9) A method in which a complex comprising an alkoxy group-containing magnesium compound and an electron donor is contacted with a titanium compound.
[0042]
(10) A method in which a complex comprising an alkoxy group-containing magnesium compound and an electron donor is contacted with an organometallic compound and then contacted with a titanium compound.
(11) A method in which a magnesium compound, an electron donor, and a titanium compound are contacted and reacted in an arbitrary order. In this reaction, each component may be pretreated with an electron donor and / or a reaction aid such as an organometallic compound or a halogen-containing silicon compound. In this method, it is preferable to use the electron donor at least once.
[0043]
(12) A method of depositing a solid magnesium-titanium complex by reacting a liquid magnesium compound having no reducing ability with a liquid titanium compound, preferably in the presence of an electron donor.
[0044]
(13) A method in which the reaction product obtained in (12) is further reacted with a titanium compound.
(14) A method in which the reaction product obtained in (11) or (12) is further reacted with an electron donor and a titanium compound.
[0045]
(15) A method of treating a solid material obtained by pulverizing a magnesium compound, preferably an electron donor, and a titanium compound, with one of halogen, a halogen compound and an aromatic hydrocarbon. Note that this method may include a step of pulverizing only the magnesium compound, the complex compound composed of the magnesium compound and the electron donor, or the magnesium compound and the titanium compound. Further, after pulverization, pretreatment with a reaction aid may be performed, and then treatment with halogen or the like may be performed. Examples of the reaction aid include organometallic compounds and halogen-containing silicon compounds.
[0046]
(16) A method in which a magnesium compound is pulverized and then contacted and reacted with a titanium compound. At this time, it is preferable to use an electron donor or a reaction aid during pulverization and / or contact / reaction.
[0047]
(17) A method of treating the compound obtained in the above (11) to (16) with a halogen, a halogen compound or an aromatic hydrocarbon.
(18) A method in which a contact reaction product with a metal oxide, organic magnesium and a halogen-containing compound is preferably contacted with an electron donor and a titanium compound.
[0048]
(19) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium or aryloxymagnesium with a titanium compound and / or a halogen-containing hydrocarbon and preferably an electron donor.
[0049]
(20) A method of contacting a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium with a titanium compound and / or an electron donor. In this case, it is preferable that a halogen-containing compound such as a halogen-containing silicon compound coexists.
[0050]
(21) A method in which a magnesium compound in a liquid state having no reducing ability and an organometallic compound are reacted to precipitate a solid magnesium / metal (aluminum) complex, and then an electron donor and a titanium compound are reacted.
[0051]
The amount of each of the above components used in preparing the solid titanium catalyst component (A) varies depending on the preparation method and cannot be specified unconditionally. For example, the electron donor is 0.01 to 5 mol per mol of the magnesium compound. The titanium compound is used in an amount of 0.01 to 1000 mol, preferably 0.1 to 200 mol.
[0052]
The solid titanium catalyst component (A) thus obtained contains magnesium, titanium, halogen and an electron donor.
In the solid titanium catalyst component (A), the halogen / titanium (atomic ratio) is about 2 to 200, preferably about 4 to 100, and the electron donor / titanium (molar ratio) is about 0.01 to 100. , Preferably about 0.2 to 10, and magnesium / titanium (atomic ratio) is about 1 to 100, preferably about 2 to 50.
[0053]
(B) Organometallic compound
In the present invention, as the organometallic compound (B), specifically, the following organometallic compounds of Group I to Group III of the periodic table are used.
[0054]
(B-1) General formula R¹ _mAl (OR²)_nH_pX_q
(Wherein R¹And R²Is a hydrocarbon group usually containing 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different. X represents a halogen atom, 0 <m ≦ 3, n is 0 ≦ n <3, p is a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). Organoaluminum compound.
[0055]
(B-2) General formula M¹AlR¹ _Four
(Where M¹Are Li, Na, K and R¹Is the same as above, and is a complex alkylated product of a Group I metal and aluminum.
[0056]
(B-3) General formula R¹R²M²
(Wherein R¹And R²Is the same as above, and M² Is Mg, Zn, or Cd).
[0057]
Examples of the organoaluminum compound belonging to the above (B-1) include the following compounds.
General formula R¹ _mAl (OR²)_3-m
(Wherein R¹And R²Is the same as above, and m is preferably a number of 1.5 ≦ m ≦ 3),
General formula R¹ _mAlX_3-m
(Wherein R¹ Is the same as above, X is halogen, m is preferably 0 <m <3),
General formula R¹ _mAlH_3-m
(Wherein R¹ Is the same as above, and m is preferably 2 ≦ m <3),
General formula R¹ _mAl (OR²)_nX_q
(Wherein R¹And R²And X is halogen, 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).
[0058]
As an aluminum compound belonging to (B-1), more specifically,
Trialkylaluminum such as triethylaluminum, tributylaluminum,
Trialkenyl aluminum such as triisoprenyl aluminum,
Dialkylaluminum alkoxides such as diethylaluminum ethoxide, dibutylaluminum butoxide,
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide,
R¹ _2.5Al (OR²)_0.5A partially alkoxylated alkylaluminum having an average composition represented by
Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide,
Partially halogenated alkylaluminums such as alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide ,
Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride,
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride,
Mention may be made of partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide.
[0059]
Moreover, as a compound similar to (B-1), the organoaluminum compound which two or more aluminum couple | bonded through the oxygen atom or the nitrogen atom can be mentioned. Examples of such compounds include:
(C₂H_Five)₂AlOAl (C₂H_Five)₂,
(C_FourH₉)₂AlOAl (C_FourH₉)₂,
(C₂H_Five)₂AlN (C₂H_Five) Al (C₂H_Five)₂In addition to
Mention may also be made of aluminoxanes such as methylaluminoxane.
[0060]
As the compound belonging to (B-2),
LiAl (C₂H_Five)_Four,
LiAl (C₇H₁₅)_FourAnd so on.
[0061]
Of these, organoaluminum compounds are preferably used.
(C) electron donor
In the present invention, as an electron donor (C), an organosilicon compound (ci) and a compound having two or more ether bonds existing through a plurality of atoms (hereinafter also referred to as “polyether compound”) (c-ii) ) Can be used.
[0062]
(ci) Organosilicon compound
The organosilicon compound used in the present invention is represented by the following formula (i).
R^a _n-Si- (OR^b)_4-n          … (I)
(Wherein n is 1, 2 or 3;
When n is 1, R^aIs a secondary or tertiary hydrocarbon group,
When n is 2 or 3, R^aAt least one of them is a secondary or tertiary hydrocarbon group, and R^aCan be the same or different,
R^bIs a hydrocarbon group having 1 to 4 carbon atoms, and when 4-n is 2 or 3, OR^bMay be the same or different. )
In the organosilicon compound represented by the formula (i), the secondary or tertiary hydrocarbon group may be a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a group having a substituent, or adjacent to Si. Examples thereof include hydrocarbon groups in which the carbon is secondary or tertiary. More specifically,
Examples of the substituted cyclopentyl group include 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 2-n-butylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2,4-dimethylcyclopentyl group, 2, 5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,3,5-trimethylcyclopentyl group, 2,3,4-triethylcyclopentyl group, tetramethylcyclopentyl group, tetraethyl A cyclopentyl group having an alkyl group such as a cyclopentyl group can be exemplified.
[0063]
Examples of the substituted cyclopentenyl group include 2-methylcyclopentenyl group, 3-methylcyclopentenyl group, 2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2,4- Dimethylcyclopentenyl group, 2,5-dimethylcyclopentenyl group, 2,3,4-trimethylcyclopentenyl group, 2,3,5-trimethylcyclopentenyl group, 2,3,4-triethylcyclopentenyl group, tetramethylcyclo Examples include cyclopentenyl groups having an alkyl group such as a pentenyl group and a tetraethylcyclopentenyl group.
[0064]
Examples of the substituted cyclopentadienyl group include 2-methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentadienyl group, 2,3 -Dimethylcyclopentadienyl group, 2,4-dimethylcyclopentadienyl group, 2,5-dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3,4-trimethylcyclopenta Dienyl group, 2,3,5-trimethylcyclopentadienyl group, 2,3,4-triethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, 2,3, Alkyl groups such as 4,5-tetraethylcyclopentadienyl group, 1,2,3,4,5-pentamethylcyclopentadienyl group, 1,2,3,4,5-pentaethylcyclopentadienyl group A cyclopentadienyl group having
[0065]
Examples of the hydrocarbon group in which the carbon adjacent to Si is a secondary carbon include i-propyl group, s-butyl group, s-amyl group, α-methylbenzyl group, etc., and adjacent to Si. Examples of the hydrocarbon group in which the carbon is a tertiary carbon include a t-butyl group, a t-amyl group, an α, α′-dimethylbenzyl group, and an admantyl group.
[0066]
Specifically, as the organosilicon compound represented by the formula (i), when n is 1, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxy Trialkoxysilanes such as silane, cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane Is exemplified.
[0067]
When n is 2, dicyclopentyldiethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, cyclohexylmethyldiethoxysilane, t-butylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyl Examples thereof include dialkoxysilanes such as dimethoxysilane and 2-norbornanemethyldimethoxysilane.
[0068]
In addition, when n is 2, a dimethoxy compound represented by the following formula (ii) is also particularly exemplified.
[0069]
[Chemical 2]
[0070]
Where R^aAnd R^cEach independently represents a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or a carbon adjacent to Si is a secondary carbon or a tertiary carbon. A certain hydrocarbon group is shown.
[0071]
As such an organosilicon compound represented by the formula (ii), for example,
Dicyclopentyldimethoxysilane,
Dicyclopentenyl dimethoxysilane,
Dicyclopentadienyldimethoxysilane,
Di-t-butyldimethoxysilane,
Di (2-methylcyclopentyl) dimethoxysilane,
Di (3-methylcyclopentyl) dimethoxysilane,
Di (2-ethylcyclopentyl) dimethoxysilane,
Di (2,3-dimethylcyclopentyl) dimethoxysilane,
Di (2,4-dimethylcyclopentyl) dimethoxysilane,
Di (2,5-dimethylcyclopentyl) dimethoxysilane,
Di (2,3-diethylcyclopentyl) dimethoxysilane,
Di (2,3,4-trimethylcyclopentyl) dimethoxysilane,
Di (2,3,5-trimethylcyclopentyl) dimethoxysilane,
Di (2,3,4-triethylcyclopentyl) dimethoxysilane,
Di (tetramethylcyclopentyl) dimethoxysilane,
Di (tetraethylcyclopentyl) dimethoxysilane,
Di (2-methylcyclopentenyl) dimethoxysilane,
Di (3-methylcyclopentenyl) dimethoxysilane,
Di (2-ethylcyclopentenyl) dimethoxysilane,
Di (2-n-butylcyclopentenyl) dimethoxysilane,
Di (2,3-dimethylcyclopentenyl) dimethoxysilane,
Di (2,4-dimethylcyclopentenyl) dimethoxysilane,
Di (2,5-dimethylcyclopentenyl) dimethoxysilane,
Di (2,3,4-trimethylcyclopentenyl) dimethoxysilane,
Di (2,3,5-trimethylcyclopentenyl) dimethoxysilane,
Di (2,3,4-triethylcyclopentenyl) dimethoxysilane,
Di (tetramethylcyclopentenyl) dimethoxysilane,
Di (tetraethylcyclopentenyl) dimethoxysilane,
Di (2-methylcyclopentadienyl) dimethoxysilane,
Di (3-methylcyclopentadienyl) dimethoxysilane,
Di (2-ethylcyclopentadienyl) dimethoxysilane,
Di (2-n-butylcyclopentadienyl) dimethoxysilane,
Di (2,3-dimethylcyclopentadienyl) dimethoxysilane,
Di (2,4-dimethylcyclopentadienyl) dimethoxysilane,
Di (2,5-dimethylcyclopentadienyl) dimethoxysilane,
Di (2,3-diethylcyclopentadienyl) dimethoxysilane,
Di (2,3,4-trimethylcyclopentadienyl) dimethoxysilane,
Di (2,3,5-trimethylcyclopentadienyl) dimethoxysilane,
Di (2,3,4-triethylcyclopentadienyl) dimethoxysilane,
Di (2,3,4,5-tetramethylcyclopentadienyl) dimethoxysilane,
Di (2,3,4,5-tetraethylcyclopentadienyl) dimethoxysilane,
Di (1,2,3,4,5-pentamethylcyclopentadienyl) dimethoxysilane,
Di (1,2,3,4,5-pentaethylcyclopentadienyl) dimethoxysilane,
Di-t-amyl-dimethoxysilane,
Di (α, α'-dimethylbenzyl) dimethoxysilane,
Di (admantyl) dimethoxysilane,
Admantyl-t-butyldimethoxysilane,
Cyclopentyl-t-butyldimethoxysilane,
Diisopropyldimethoxysilane,
Di-s-butyldimethoxysilane,
Di-s-amyldimethoxysilane,
And isopropyl-s-butyldimethoxysilane.
[0072]
When n is 3,
Monoalkoxysilanes such as tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane, etc. Can be mentioned.
[0073]
Further, as the organosilicon compound (c-i), an organosilicon compound represented by the following formula (iii) can also be used.
R_nSi (OR ’)_4-n            ... (iii)
(Wherein R and R ′ are hydrocarbon groups, 0 <n <4)
As such an organosilicon compound represented by the general formula (i), specifically,
Trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bism-tolyldimethoxysilane, bisp-tolyldimethoxysilane, bisp -Tolyldiethoxysilane, bisethylphenyldimethoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, decyltrimethoxysilane, decyl Triethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltriallyloxysilane, etc.
[0074]
Further, compounds similar to the organosilicon compound represented by the formula (iii) include γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyl silicate, butyl silicate, vinyl tris (β -Methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane and the like.
[0075]
The organosilicon compound represented by the formula (iii) and the organosilicon compound represented by the formula (i) may be the same.
You may use these in combination of 2 or more types.
[0076]
In the present invention, among these, dimethoxysilanes, particularly dimethoxysilanes represented by the formula (ii) are preferred, and specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) Dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di-t-amyldimethoxysilane and the like are preferable.
[0077]
(c-ii) Polyether compounds
In a compound having two or more ether bonds (polyether compound) existing through a plurality of atoms used in the present invention, the atoms present between these ether bonds are carbon, silicon, oxygen, sulfur, phosphorus, boron It is 1 or more types selected from the group which consists of, and an atom number is 2 or more. Among these, a relatively bulky substituent at an atom between ether bonds, specifically, a substituent having 2 or more carbon atoms, preferably 3 or more and having a linear, branched or cyclic structure, more preferably a branched group. Those having a substituent having a ring-like or cyclic structure are desirable. Further, a compound in which a plurality of, preferably 3 to 20, more preferably 3 to 10, and particularly preferably 3 to 7 carbon atoms are contained in atoms present between two or more ether bonds is preferable.
[0078]
Examples of such a polyether compound (c-ii) include a compound represented by the following formula.
[0079]
[Chemical 3]
[0080]
In the formula, n is an integer of 2 ≦ n ≦ 10, and R¹~ R²⁶Is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any R¹~ R²⁶, Preferably R¹~ R²ⁿMay jointly form a ring other than a benzene ring, and atoms other than carbon may be contained in the main chain.
[0081]
As the polyether compound (c-ii) as described above, specifically,
2- (2-ethylhexyl) -1,3-dimethoxypropane,
2-isopropyl-1,3-dimethoxypropane,
2-butyl-1,3-dimethoxypropane,
2-s-butyl-1,3-dimethoxypropane,
2-cyclohexyl-1,3-dimethoxypropane,
2-phenyl-1,3-dimethoxypropane,
2-cumyl-1,3-dimethoxypropane,
2- (2-phenylethyl) -1,3-dimethoxypropane,
2- (2-cyclohexylethyl) -1,3-dimethoxypropane,
2- (p-chlorophenyl) -1,3-dimethoxypropane,
2- (diphenylmethyl) -1,3-dimethoxypropane,
2- (1-naphthyl) -1,3-dimethoxypropane,
2- (2-fluorophenyl) -1,3-dimethoxypropane,
2- (1-decahydronaphthyl) -1,3-dimethoxypropane,
2- (p-t-butylphenyl) -1,3-dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane,
2,2-dicyclopentyl-1,3-dimethoxypropane,
2,2-diethyl-1,3-dimethoxypropane,
2,2-dipropyl-1,3-dimethoxypropane,
2,2-diisopropyl-1,3-dimethoxypropane,
2,2-dibutyl-1,3-dimethoxypropane,
2-methyl-2-propyl-1,3-dimethoxypropane,
2-methyl-2-benzyl-1,3-dimethoxypropane,
2-methyl-2-ethyl-1,3-dimethoxypropane,
2-methyl-2-isopropyl-1,3-dimethoxypropane,
2-methyl-2-phenyl-1,3-dimethoxypropane,
2-methyl-2-cyclohexyl-1,3-dimethoxypropane,
2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane,
2,2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane,
2-methyl-2-isobutyl-1,3-dimethoxypropane,
2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxypropane,
2,2-diphenyl-1,3-dimethoxypropane,
2,2-dibenzyl-1,3-dimethoxypropane,
2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane,
2,2-diisobutyl-1,3-diethoxypropane,
2,2-diisobutyl-1,3-dibutoxypropane,
2-isobutyl-2-isopropyl-1,3-dimethoxypropane,
2- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane,
2- (1-methylbutyl) -2-s-butyl-1,3-dimethoxypropane,
2,2-di-s-butyl-1,3-dimethoxypropane,
2,2-di-t-butyl-1,3-dimethoxypropane,
2,2-dineopentyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethoxypropane,
2-phenyl-2-isopropyl-1,3-dimethoxypropane,
2-phenyl-2-s-butyl-1,3-dimethoxypropane,
2-benzyl-2-isopropyl-1,3-dimethoxypropane,
2-benzyl-2-s-butyl-1,3-dimethoxypropane,
2-phenyl-2-benzyl-1,3-dimethoxypropane,
2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane,
2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane,
2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane,
2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane,
2-isopropyl-2-s-butyl-1,3-dimethoxypropane,
2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane,
2,3-diphenyl-1,4-diethoxybutane,
2,3-dicyclohexyl-1,4-diethoxybutane,
2,2-dibenzyl-1,4-diethoxybutane,
2,3-dicyclohexyl-1,4-diethoxybutane,
2,3-diisopropyl-1,4-diethoxybutane,
2,2-bis (p-methylphenyl) -1,4-dimethoxybutane,
2,3-bis (p-chlorophenyl) -1,4-dimethoxybutane,
2,3-bis (p-fluorophenyl) -1,4-dimethoxybutane,
2,4-diphenyl-1,5-dimethoxypentane,
2,5-diphenyl-1,5-dimethoxyhexane,
2,4-diisopropyl-1,5-dimethoxypentane,
2,4-diisobutyl-1,5-dimethoxypentane,
2,4-diisoamyl-1,5-dimethoxypentane,
3-methoxymethyltetrahydrofuran,
3-methoxymethyldioxane,
1,3-diisobutoxypropane,
1,2-diisobutoxypropane,
1,2-diisobutoxyethane,
1,3-diisoamyloxypropane,
1,3-diisoneopentyloxyethane,
1,3-dineopentyroxypropane,
2,2-tetramethylene-1,3-dimethoxypropane,
2,2-pentamethylene-1,3-dimethoxypropane,
2,2-hexamethylene-1,3-dimethoxypropane,
1,2-bis (methoxymethyl) cyclohexane,
2,8-dioxaspiro [5,5] undecane,
3,7-dioxabicyclo [3,3,1] nonane,
3,7-dioxabicyclo [3,3,0] octane,
3,3-diisobutyl-1,5-oxononane,
6,6-diisobutyldioxyheptane,
1,1-dimethoxymethylcyclopentane,
1,1-bis (dimethoxymethyl) cyclohexane,
1,1-bis (methoxymethyl) bicyclo [2,2,1] heptane,
1,1-dimethoxymethylcyclopentane,
2-methyl-2-methoxymethyl-1,3-dimethoxypropane,
2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane,
2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxycyclohexane,
2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane,
2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane,
2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane,
2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane,
2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane,
2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,
2-isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane,
2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,
2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane,
2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,
Tris (p-methoxyphenyl) phosphine,
Methylphenylbis (methoxymethyl) silane,
Diphenylbis (methoxymethyl) silane,
Methylcyclohexylbis (methoxymethyl) silane,
Di-t-butylbis (methoxymethyl) silane,
Cyclohexyl-t-butylbis (methoxymethyl) silane,
Examples include i-propyl-t-butylbis (methoxymethyl) silane.
[0082]
These can also be used in combination of two or more.
Of these, 1,3-diethers are preferably used.
2,2-diisobutyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethoxypropane (IPAMP),
2,2-dicyclohexyl-1,3-dimethoxypropane,
2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane,
2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane,
2-isopropyl-2-s-butyl-1,3-dimethoxypropane,
2,2-diphenyl-1,3-dimethoxypropane,
2-Cyclopentyl-2-isopropyl-1,3-dimethoxypropane is preferably used.
[0083]
In the present invention, the above-mentioned organosilicon compound (c-i) and polyether compound (c-ii) can be used in combination as the electron donor (C).
Further, as the electron donor (C), another electron donor (b) can be used in combination with the organosilicon compound (c-i) and / or the polyether compound (c-ii).
[0084]
Specific examples of such other electron donors (b) include the electron donor (a) shown in preparing the solid titanium catalyst component (A), the following nitrogen-containing compounds, and the like. And oxygen-containing compounds and phosphorus-containing compounds.
[0085]
Specific examples of nitrogen-containing compounds that can be used as the electron donor (b) include 2,6-substituted piperidines, 2,5-substituted piperidines, N, N, N ′, N′-tetramethyl. Examples thereof include substituted methylenediamines such as methylenediamine, N, N, N ′, N′-tetraethylmethylenediamine, 1,3-dibenzylimidazolidine, and 1,3-dibenzyl-2-phenylimidazolidine.
[0086]
Specific examples of phosphorus-containing compounds include triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite. And phosphites such as
[0087]
Specific examples of the oxygen-containing compound include 2,6-substituted tetrahydropyrans and 2,5-substituted tetrahydropyrans.
Production of propylene-based block copolymer [I]
The propylene-based block copolymer [I] used in the present invention is formed from (A) a solid titanium catalyst component, (B) an organometallic compound, and (C) an electron donor as required. It is produced using an olefin polymerization catalyst (1).
[0088]
In the present invention, the catalyst component for forming such an olefin polymerization catalyst (1) can be used after preliminarily polymerizing an olefin having 2 or more carbon atoms to form a prepolymerized catalyst.
[0089]
As the olefin having 2 or more carbon atoms to be prepolymerized, specifically,
Linear α- such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene Olefins,
Cyclopentene, cycloheptene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octa Cycloolefins such as hydronaphthalene,
Further, olefins represented by the following formulas (i) and (ii) can be mentioned.
[0090]
[Formula 4]
[0091]
Examples of the cycloalkyl group represented by X include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
[0092]
Also R¹, R²And R^ThreeExamples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an aryl group such as a phenyl group and a naphthyl group, and a norbornyl group. R¹, R²And R^ThreeThe hydrocarbon group represented by may contain silicon and halogen.
[0093]
As such a compound represented by the formula (i) or (ii), specifically,
3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, Branched α-olefins such as 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene,
Examples include vinyl compounds such as allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, and allyltrialkylsilanes.
[0094]
Of these, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-hexene, vinylcyclohexane, allyltrimethylsilane, dimethylstyrene and the like are preferable. , Propylene, 3-methyl-1-butene, vinylcyclohexyne, and allyltrimethylsilane are more preferable.
[0095]
These may be a combination of two or more.
In the present invention, it is preferable to prepolymerize the olefin as described above in an amount of 0.01 to 2000 g, preferably 0.1 to 200 g, per 1 g of the solid titanium catalyst component (A) to form a prepolymerized catalyst.
[0096]
The concentration of the solid titanium catalyst component (A) in the prepolymerization system is usually about 0.01 to 200 mmol, preferably about 0.05 to 100 mmol, in terms of titanium atoms, per liter of polymerization volume.
[0097]
The organometallic compound catalyst component (B) can be used in an amount of usually 0.1 to 100 moles, preferably 0.5 to 50 moles per mole of titanium atoms in the solid titanium catalyst component (A).
[0098]
The electron donor (C) can be used as needed in an amount of usually 0.1 to 50 moles, preferably 0.5 to 30 moles, more preferably 1 to 10 moles per mole of titanium atom.
[0099]
The prepolymerization can be performed under mild conditions by adding the olefin and the catalyst component as described above in the presence of, for example, a polymerization-inert hydrocarbon medium.
Specific examples of the hydrocarbon medium used here include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane, cyclohexane, and methylcyclohexane. Alicyclic hydrocarbons such as pentane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; petroleum fractions such as gasoline, kerosene and light oil; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, or these Combinations are listed. Of these, it is particularly preferable to use an aliphatic hydrocarbon.
[0100]
The reaction temperature during the prepolymerization is preferably such that the prepolymer to be produced does not substantially dissolve in the inert hydrocarbon medium, usually about −20 to + 100 ° C., preferably about −20 to It is desirable that the temperature is + 80 ° C, more preferably 0 to + 40 ° C.
[0101]
In the prepolymerization, a molecular weight regulator such as hydrogen can be used. In addition to the above components, other compounds useful for forming a prepolymerization catalyst can be used as necessary.
[0102]
The prepolymerization may be performed by any of batch, semi-continuous and continuous methods. The propylene-based block copolymer [I] used in the present invention, in the presence of the olefin polymerization catalyst (1) or the prepolymerization catalyst as described above,
[I-1] a step of producing a crystalline polypropylene component by homopolymerizing propylene or copolymerizing propylene and another α-olefin;
[I-2] The step of producing a low crystalline or non-crystalline ethylene / propylene copolymer component by copolymerizing ethylene and propylene can be obtained in any order.
[0103]
Specifically, in the presence of an olefin polymerization catalyst (1) or a prepolymerization catalyst, first, [I-1] propylene is homopolymerized, or propylene and another α-olefin are copolymerized to form crystalline polypropylene. Propylene-based block copolymer is formed by forming a component and then copolymerizing [I-2] ethylene and propylene to form a low crystalline or amorphous ethylene / propylene copolymer component. Can do.
[0104]
[I-2] Copolymerizes ethylene and propylene to form a low crystalline or amorphous ethylene / propylene copolymer component, and then [I-1] homopolymerizes propylene, propylene and others A propylene-based block copolymer can also be produced by copolymerizing with an α-olefin to form a crystalline polypropylene component.
[0105]
In the present invention, the propylene-based block copolymer [I] forms [I-1] a crystalline polypropylene component, and then [I-2] a low crystalline or amorphous ethylene / propylene copolymer component. It is preferable to manufacture by forming, and this will be mainly described below.
[0106]
In the step [I-1] of forming a crystalline polypropylene component, propylene is homopolymerized or copolymerized with other α-olefins in the presence of an olefin polymerization catalyst (1) or a prepolymerization catalyst. I am letting.
[0107]
Examples of such other α-olefins include ethylene and α-olefins having 4 to 10 carbon atoms such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene. 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1 -Pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and the like.
[0108]
Furthermore, within the range not impairing the object of the present invention, olefins other than α-olefins as shown as prepolymerized olefins, and further diene compounds as shown in the later-described ethylene / propylene copolymerization step [I-2] Can also be used in small amounts. Two or more of these can be used in combination.
[0109]
Such units derived from olefins other than propylene can be used so that they are finally present in the polypropylene component in an amount of 5 mol%, preferably 4 mol% or less.
[0110]
In the present invention, it is preferable to homopolymerize propylene in this step [I-1].
In the present invention, this step [I-1] can be carried out in two or more stages by changing the reaction conditions.
[0111]
In the step [I-1] of forming the crystalline polypropylene component, the solid titanium catalyst component (A) or the prepolymerized catalyst is preferably about 0.0001 to 50 mmol in terms of titanium atom per liter of polymerization volume, preferably It is preferably used in an amount of about 0.001 to 10 mmol.
[0112]
The organometallic compound (B) can be used in an amount of 1 to 2000 moles, preferably 2 to 1000 moles per mole of titanium atoms in the solid titanium catalyst component (A). The electron donor (C) can be used as needed in an amount of 0.001 to 5000 moles, preferably 0.05 to 1000 moles per mole of titanium atoms.
[0113]
When a prepolymerization catalyst is used at the time of this polymerization, the use of the organometallic compound (B) and the electron donor (C) is optional and may or may not be used. It can be used in an amount as described above with respect to the concentration of titanium atoms in the system.
[0114]
Further, the electron donor (C) added as required in the (main) polymerization may be the same as or different from the electron donor (C) used in forming the prepolymerization catalyst.
[0115]
The polymerization process of propylene can be carried out by a solvent suspension polymerization method, a suspension polymerization method using liquid propylene as a solvent, a gas phase polymerization method, etc., and in any of batch, semi-continuous and continuous methods Can also be done.
[0116]
In carrying out the solvent suspension polymerization method, a polymerization-inactive hydrocarbon can be used as a polymerization solvent. Specific examples of such inert hydrocarbons include hydrocarbons as shown in the preliminary polymerization, and aliphatic hydrocarbons are preferred.
[0117]
The step [I-1] as described above is usually performed at a temperature of about −50 to 200 ° C., preferably about 50 to 100 ° C., and usually normal pressure to 100 kg / cm.²Preferably about 2-50Kg / cm²Under the pressure of
[0118]
In this step [I-1], the molecular weight of the resulting polypropylene can be adjusted using hydrogen (chain transfer agent).
In the present invention, after producing a crystalline polypropylene component as described above, ethylene and propylene are then copolymerized without carrying out the catalyst deactivation treatment used in the production of the polypropylene component, so that low crystalline or non-crystalline A crystalline ethylene / propylene copolymer component is produced to produce a propylene-based block copolymer.
[0119]
In the copolymerization step [I-2] of ethylene and propylene, other olefins such as those shown for the crystalline polypropylene component [I-1] are used as long as the object of the present invention is not impaired. A small amount of a diene compound can also be used.
[0120]
As such a diene compound, for example,
1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl- 1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl- 1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl- 1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclo Examples include pentadiene. These can be used in combination of two or more.
[0121]
In the copolymerization system of ethylene and propylene, the polypropylene component is used in an amount of 10 to 1000 g, preferably 10 to 800 g, particularly preferably 30 to 500 g, per liter of polymerization volume. The amount of this polypropylene is usually 0.0001 to 1 mmol, preferably about 0.001 to 0.5, per 1 liter of polymerization volume, in terms of titanium atoms of the solid catalyst component (A) contained in the polypropylene. Preferably it is millimolar.
[0122]
In the present invention, a catalyst component can be further added to the copolymerization system of ethylene and propylene carried out in the presence of the polypropylene component containing the olefin polymerization catalyst (1). When the catalyst component is added, the solid titanium catalyst component (A) is in an amount of 0.0001 to 20 mmol, preferably 0.001 to 20 mmol, per liter of polymerization volume, and the electron donor (C) is The organometallic compound (B) is used in an amount of 0.001 to 5000 mol, preferably 0.01 to 1000 mol, per mol of titanium atom in the polymerization system, and 1 to 2000 mol per mol of titanium atom in the polymerization system. Preferably, it can be used appropriately in an amount of about 2 to 1000 mol.
[0123]
The copolymerization of ethylene and propylene as described above may be carried out by a gas phase method or a liquid phase method, and can be carried out by any of batch, semi-continuous and continuous methods. Further, this copolymerization can be carried out in two or more stages by changing the reaction conditions.
[0124]
When the copolymerization is performed by a solvent suspension polymerization method, the above-described inert hydrocarbon can be used as a polymerization solvent.
The copolymerization step [I-2] of ethylene and propylene is usually at a polymerization temperature of about −50 to 200 ° C., preferably about 20 to 100 ° C., and usually normal pressure to 100 kg / cm.², Preferably about 2-50 kg / cm²Under the pressure of
[0125]
At the time of copolymerization, hydrogen (chain transfer agent) can be added as necessary to adjust the molecular weight.
When the propylene-based block copolymer [I] is produced using the prepolymerization catalyst as described above, the unit derived from the olefin formed by the prepolymerization (prepolymer) is finally The resulting propylene-based block copolymer [I] preferably contains 0.001 to 3% by weight, preferably 0.005 to 2% by weight.
[0126]
The propylene block copolymer [I] obtained as described above has a highly stereoregular polypropylene component.
The stereoregularity of the propylene-based block copolymer [I] can be determined, for example, from the boiling heptane insoluble component amount in the n-decane insoluble component of the copolymer.
[0127]
The amount of boiling heptane-insoluble component (in the n-decane insoluble component) of the propylene-based block copolymer [I] used in the present invention is preferably 80 to 100% by weight, and more preferably 85 to 100% by weight.
[0128]
The molecular weight of the rubber component can be measured as the intrinsic viscosity [η] of the n-decane soluble component, and is desirably 0.2 to 20 dl / g, preferably 0.5 to 15 dl / g.
[0129]
Moreover, since the yield of the propylene-based block copolymer [I] is high with respect to the solid titanium catalyst component unit amount, the catalyst residue in the product, in particular, the halogen content can be relatively reduced. Therefore, the operation of removing the catalyst in the product can be omitted, and rusting of the mold is suppressed when molding the olefin polymer composition formed from the obtained propylene-based block copolymer [I]. can do.
[0130]
Ethylene copolymer [ II ]
The low crystalline or non-crystalline ethylene copolymer [II] forming the olefin polymer composition according to the present invention is:
It can be obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst (2).
[0131]
(D) Transition metal compound
The transition metal compound (D) (hereinafter also referred to as metallocene compound (D)) containing a ligand having a cyclopentadienyl skeleton used in the present invention is represented by the following formula (1).
[0132]
ML_x                    … (1)
In the formula, M is a transition metal selected from Group IVB of the Periodic Table, specifically zirconium, titanium or hafnium, preferably zirconium.
[0133]
L is a ligand coordinated to the transition metal, at least one L is a group having a cyclopentadienyl skeleton, and x is the valence of the transition metal.
Examples of the group having a cyclopentadienyl skeleton include
A cyclopentadienyl group,
Methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl Groups, propylcyclopentadienyl groups, methylpropylcyclopentadienyl groups, butylcyclopentadienyl groups, methylbutylcyclopentadienyl groups, hexylcyclopentadienyl groups and other alkyl-substituted cyclopentadienyl groups,
Indenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group and the like can be mentioned.
[0134]
These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.
Of these, an alkyl-substituted cyclopentadienyl group is particularly preferable.
[0135]
When the compound represented by the formula (1) has two or more groups having a cyclopentadienyl skeleton as the ligand L, the groups having two cyclopentadienyl skeletons are ethylene, propylene, etc. And a substituted alkylene group such as isopropylidene and diphenylmethylene, a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group.
[0136]
The ligand L other than the group having a cyclopentadienyl skeleton includes a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO_ThreeR group (R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom or a hydrogen atom. More specifically,
Examples of the hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, Examples thereof include alkyl groups such as octyl group, 2-ethylhexyl group and decyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, aryl groups such as phenyl group and tolyl group, and aralkyl groups such as benzyl group and neophyll group.
[0137]
Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentoxy group, hexoxy group, octoxy group and the like. ,
Examples of aryloxy groups include phenoxy groups,
Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group.
Examples of the halogen include fluorine, chlorine, bromine and iodine.
[0138]
SO_ThreeExamples of the R group include a p-toluenesulfonate group, a methanesulfonate group, and a trifluoromethanesulfonate group.
For example, when the valence of the transition metal is 4, the metallocene compound (D) is more specifically represented by the following general formula (2).
[0139]
R² _kR^Three _lR^Four _mR^Five _nM ... (2)
(In the formula, M is the same as the above formula (1),
R²Is a group (ligand) having a cyclopentadienyl skeleton,
R^Three, R^FourAnd R^FiveIs a group having a cyclopentadienyl skeleton or a group shown as another ligand in the formula (1), k is an integer of 1 or more, and k + 1 + m + n = 4. )
In the present invention, among the compounds represented by the above formula (2), R^Three, R^FourAnd R^FiveOf these, a metallocene compound in which at least one of the groups has a cyclopentadienyl skeleton, that is, a metallocene compound having at least two groups having a cyclopentadienyl skeleton is preferably used. Further, as described above, the group having two cyclopentadienyl skeletons may be bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like.
[0140]
As such a metallocene compound (D), specifically,
Bis (cyclopentadienyl) zirconium dichloride,
Bis (methylcyclopentadienyl) zirconium dichloride,
Bis (ethylcyclopentadienyl) zirconium dichloride,
Bis (n-propylcyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dichloride,
Bis (n-hexylcyclopentadienyl) zirconium dichloride,
Bis (methyl-n-propylcyclopentadienyl) zirconium dichloride,
Bis (methyl-n-butylcyclopentadienyl) zirconium dichloride,
Bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dibromide,
Bis (n-butylcyclopentadienyl) zirconium methoxychloride,
Bis (n-butylcyclopentadienyl) zirconium ethoxy chloride,
Bis (n-butylcyclopentadienyl) zirconium butoxychloride,
Bis (n-butylcyclopentadienyl) zirconium ethoxide,
Bis (n-butylcyclopentadienyl) zirconium methyl chloride,
Bis (n-butylcyclopentadienyl) zirconium dimethyl,
Bis (n-butylcyclopentadienyl) zirconium benzyl chloride,
Bis (n-butylcyclopentadienyl) zirconium dibenzyl,
Bis (n-butylcyclopentadienyl) zirconium phenyl chloride,
Bis (n-butylcyclopentadienyl) zirconium hydride chloride,
Bis (indenyl) zirconium dichloride,
Bis (indenyl) zirconium dibromide,
Bis (indenyl) zirconium bis (p-toluenesulfonate),
Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,
Bis (fluorenyl) zirconium dichloride,
Ethylenebis (indenyl) zirconium dichloride,
Ethylenebis (indenyl) zirconium dibromide,
Ethylenebis (indenyl) dimethylzirconium,
Ethylenebis (indenyl) diphenylzirconium,
Ethylenebis (indenyl) methylzirconium monochloride,
Ethylene bis (indenyl) zirconium bis (methanesulfonate),
Ethylene bis (indenyl) zirconium bis (p-toluenesulfonate),
Ethylene bis (indenyl) zirconium bis (trifluoromethanesulfonate),
Ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene bis (dimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene bis (trimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (indenyl) zirconium dichloride,
Dimethylsilylene bis (indenyl) zirconium bis (trifluoromethanesulfonate),
Dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,
Dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride,
Diphenylsilylenebis (indenyl) zirconium dichloride,
Methylphenylsilylenebis (indenyl) zirconium dichloride,
Bis (cyclopentadienyl) zirconium dichloride,
Bis (cyclopentadienyl) zirconium dibromide,
Bis (cyclopentadienyl) methylzirconium monochloride,
Bis (cyclopentadienyl) ethylzirconium monochloride,
Bis (cyclopentadienyl) cyclohexyl zirconium monochloride,
Bis (cyclopentadienyl) phenylzirconium monochloride,
Bis (cyclopentadienyl) benzylzirconium monochloride,
Bis (cyclopentadienyl) zirconium monochloride monohydride,
Bis (cyclopentadienyl) methylzirconium monohydride,
Bis (cyclopentadienyl) dimethylzirconium,
Bis (cyclopentadienyl) diphenylzirconium,
Bis (cyclopentadienyl) dibenzylzirconium,
Bis (cyclopentadienyl) zirconium methoxychloride,
Bis (cyclopentadienyl) zirconium ethoxy chloride,
Bis (cyclopentadienyl) zirconium bis (methanesulfonate),
Bis (cyclopentadienyl) zirconium bis (p-toluenesulfonate),
Bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (methylcyclopentadienyl) zirconium dichloride,
Bis (dimethylcyclopentadienyl) zirconium dichloride,
Bis (dimethylcyclopentadienyl) zirconium ethoxy chloride,
Bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (ethylcyclopentadienyl) zirconium dichloride,
Bis (methylethylcyclopentadienyl) zirconium dichloride,
Bis (propylcyclopentadienyl) zirconium dichloride,
Bis (methylpropylcyclopentadienyl) zirconium dichloride,
Bis (butylcyclopentadienyl) zirconium dichloride,
Bis (methylbutylcyclopentadienyl) zirconium dichloride,
Bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate),
Bis (trimethylcyclopentadienyl) zirconium dichloride,
Bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride,
Bis (hexylcyclopentadienyl) zirconium dichloride,
And bis (trimethylsilylcyclopentadienyl) zirconium dichloride. In the above examples, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. Including.
[0141]
Moreover, although the metallocene compound whose M is a zirconium was illustrated above, the metallocene compound which replaced the zirconium in the said compound with titanium or hafnium can also be mentioned.
[0142]
Of these,
Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
Bis (n-propylcyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-n-propylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride
Etc. are preferably used.
[0143]
In the present invention, a compound represented by the following formula (3) can also be used as the metallocene compound (D).
L^aMX₂          (3)
(M is a group IV or lanthanide series metal of the periodic table;
L^aIs a derivative of a delocalized π-bonding group, giving a constrained geometry to the metal M active site,
X is each independently hydrogen, or a hydrocarbon group, silyl group or germanyl group containing 20 or less carbon, silicon or germanium. )
Among such compounds represented by the formula (3), specifically, a compound represented by the following formula (4) is preferable.
[0144]
[Chemical formula 5]
[0145]
M is titanium or zirconium, and X is the same as described above.
Cp is a substituted cyclopentadienyl group having a π bond to M and having a substituent Z, or a derivative thereof.
[0146]
Z is oxygen, sulfur, boron or a group IVA element of the periodic table;
Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur;
Z and Y may form a condensed ring.
[0147]
As such a compound represented by the formula (4), specifically,
(Dimethyl (t-butylamide) (tetramethyl-η^Five-Cyclopentadienyl) silane) dibenzylzirconium,
(Dimethyl (t-butylamide) (tetramethyl-η^Five-Cyclopentadienyl) silane) dibenzyltitanium,
(Dimethyl (t-butylamide) (tetramethyl-η^Five-Cyclopentadienyl) silane) dimethyl titanium,
((T-Butylamide) (Tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediyl) dimethylzirconium,
((T-Butylamide) (Tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediyl) dibenzyltitanium,
((Methylamide) (Tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediyl) dibenzhydrylzirconium,
((Methylamide) (Tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediyl) dineopentyl titanium,
((Phenylphosphide) (tetramethyl-η^Five-Cyclopentadienyl) methylene) diphenyltitanium,
(Dibenzyl (t-butylamide) (tetramethyl-η^Five-Cyclopentadienyl) silane) dibenzylzirconium,
(Dimethyl (benzylamide) (η^Five-Cyclopentadienyl) silane) di (trimethylsilyl) titanium,
(Dimethyl (phenylphosphide)-(tetramethyl-η^Five-Cyclopentadienyl) silane) dibenzylzirconium,
(Dimethyl (t-butylamide) (tetramethyl-η^Five-Cyclopentadienyl) silane) dibenzylhafnium,
((Tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediyl) dibenzyltitanium,
(2-η^Five-(Tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)) dibenzyltitanium,
(2-η^Five-(Tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)) dibenzylzirconium,
(2-η^Five-(Tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)) dimethylzirconium,
(2-((4a, 4b, 8a, 9,9a-η) -9H-fluoren-9-yl) cyclohexanolate (2-)) dimethyl titanium,
(2-((4a, 4b, 8a, 9,9a-η) -9H-fluoren-9-yl) cyclohexanolate (2-)) dimethylzirconium,
(2-((4a, 4b, 8a, 9,9a-η) -9H-fluoren-9-yl) cyclohexanolate (2-)) dibenzylzirconium and the like.
[0148]
In the present invention, the above metallocene compounds (D) can be used in combination of two or more.
The (E-1) organoaluminum oxy compound forming the olefin polymerization catalyst (2) used in the present invention may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. A benzene-insoluble organoaluminum oxy compound may also be used.
[0149]
A conventionally well-known aluminoxane can be manufactured by the following methods, for example.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to and reacted with a suspension of the above hydrocarbon medium.
(2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.
[0150]
The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.
[0151]
Specifically, as an organoaluminum compound used when preparing an aluminoxane,
Trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecyl Trialkylaluminum such as aluminum,
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum,
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride,
Dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride,
Dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide,
Examples thereof include dialkylaluminum aryloxides such as diethylaluminum phenoxide.
[0152]
Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
Further, as an organoaluminum compound used for preparing an aluminoxane, isoprenylaluminum represented by the following general formula can also be used.
[0153]
(I-C_FourH₉)_xAl_y(C_FiveH_Ten)_z      … [II]
(In the formula, x, y, and z are positive numbers, and z ≧ 2x.)
The above organoaluminum compounds are used alone or in combination.
[0154]
Solvents used in aluminoxane solutions or suspensions include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, and aliphatic carbonization such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane. Hydrogen, cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are mentioned. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.
[0155]
Further, the benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms. It is insoluble or hardly soluble.
[0156]
Examples of the Lewis acid or ionic compound (E-2) forming the olefin polymerization catalyst (2) include JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, and JP-A-3-17905. Examples include Lewis acids, ionic compounds, and carborane compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and US-547718.
[0157]
Specifically, as the Lewis acid, BR_Three(R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group, trifluoromethyl group, etc.), for example,
Trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p- Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.
[0158]
Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.
[0159]
Specifically, as the trialkyl-substituted ammonium salt, for example,
Triethylammonium tetra (phenyl) boron,
Tripropylammonium tetra (phenyl) boron,
Tri (n-butyl) ammonium tetra (phenyl) boron,
Trimethylammonium tetra (p-tolyl) boron,
Trimethylammonium tetra (o-tolyl) boron,
Tributylammonium tetra (pentafluorophenyl) boron,
Tripropylammonium tetra (o, p-dimethylphenyl) boron,
Tributylammonium tetra (m, m-dimethylphenyl) boron,
Tributylammonium tetra (p-trifluoromethylphenyl) boron,
Examples include tri (n-butyl) ammonium tetra (o-tolyl) boron.
[0160]
Examples of N, N-dialkylanilinium salts include
N, N-dimethylanilinium tetra (phenyl) boron,
N, N-diethylanilinium tetra (phenyl) boron,
And N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron.
[0161]
Examples of dialkyl ammonium salts include
Di (1-propyl) ammonium tetra (pentafluorophenyl) boron,
Examples include dicyclohexylammonium tetra (phenyl) boron.
[0162]
Furthermore, examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) boronate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate and the like.
[0163]
Further, examples of the ionic compound include the following compounds.
Bis [tri (n-butyl) ammonium] nonaborate,
Bis [tri (n-butyl) ammonium] decaborate,
Bis [tri (n-butyl) ammonium] undecaborate,
Bis [tri (n-butyl) ammonium] dodecaborate,
Bis [tri (n-butyl) ammonium] decachlorodecaborate,
Bis [tri (n-butyl) ammonium] dodecachlorododecaborate,
Tri (n-butyl) ammonium 1-carbadecaborate,
Tri (n-butyl) ammonium 1-carbaundecaborate,
Tri (n-butyl) ammonium 1-carbadodecaborate,
Tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate,
Salts of anions such as tri (n-butyl) ammonium bromo-1-carbadodecaborate (in addition to the above examples where the counter ion is tri (n-butyl) ammonium, but the counter ion is not limited to this) Not)
Decaborane (14),
7,8-dicarboundecaborane (13),
2,7-dicarboundecaborane (13),
Undecahydride-7,8-dimethyl-7,8-dicarboundecarborane,
Dodecahydride-11-methyl-2,7-dicarboundecarborane,
Tri (n-butyl) ammonium 6-carbadecaborate (14),
Tri (n-butyl) ammonium 6-carbadecaborate (12),
Tri (n-butyl) ammonium 7-carbaundecaborate (13),
Tri (n-butyl) ammonium 7,8-dicarbaundecaborate (12),
Tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate,
Tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate,
Tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate,
Tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate,
Tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate,
Boranes such as tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate, salts of carborane complexes or carborane anions,
4-carbanonaborane (14),
1,3-dicarbanonaborane (13),
6,9-dicarbadecarborane (14),
Dodecahydride-1-phenyl-1,3-dicarbanonaborane,
Dodecahydride-1-methyl-1,3-dicarbanonaborane,
Carboranes or salts of carboranes such as undecahydride-1,3-dimethyl-1,3-dicarbanonaborane,
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III),
Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (III),
Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III),
Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III),
Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III),
Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III),
Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecarboxylate) ferrate (III),
Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecarboxylate) chromate (III),
Tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III),
Tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III),
Bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III),
Tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III),
Bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (IV),
Bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III),
Examples thereof include a metal carborane salt such as bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) or a metal borane anion.
[0164]
Two or more of the above compounds may be used in combination.
In the present invention, when the olefin polymerization catalyst (2) is formed, the organoaluminum oxy compound (E-1) and Lewis acid or ionic compound (E-2) can be used in combination.
[0165]
In the present invention, when forming the olefin polymerization catalyst (2), together with the metallocene compound (D), organoaluminum oxy compound (E-1) and / or Lewis acid or ionic compound (E-2) If necessary, an organoaluminum compound, a carrier and the like can also be used.
[0166]
Specific examples of the organoaluminum compound include those similar to the compounds shown as the organoaluminum compound (B) when forming the olefin polymerization catalyst (1).
[0167]
The carrier used in the present invention is an inorganic or organic compound, and a granular or particulate solid having a particle size of 10 to 300 μm, preferably 20 to 200 μm is used. Of these, porous oxides are preferred as the inorganic carrier, specifically, SiO.₂, Al₂O_Three, MgO, ZrO₂TiO₂, B₂O_Three, CaO, ZnO, BaO, ThO₂Or mixtures thereof, such as SiO₂-MgO, SiO₂-Al₂O_Three, SiO₂-TiO₂, SiO₂-V₂O_Five, SiO₂-Cr₂O_Three, SiO₂-TiO₂-MgO etc. can be illustrated. Among these, SiO₂And Al₂O_ThreeThe main component is at least one component selected from the group consisting of:
[0168]
The inorganic oxide contains a small amount of Na.₂CO_Three, K₂CO_Three, CaCO_Three, MgCO_Three, Na₂SO_Four, Al₂(SO_Four)_Three, BaSO_Four, KNO_Three, Mg (NO_Three)₂, Al (NO_Three)_Three, Na₂O, K₂O, Li₂It may contain carbonates such as O, sulfates, nitrates and oxide components.
[0169]
Such a carrier has a specific surface area of 50 to 1000 m, although its properties vary depending on the type and production method.²/ G, preferably 100-700m²/ G, and the pore volume is 0.3 to 2.5 cm.²/ G is desirable. Moreover, this support | carrier is used by baking at 100-1000 degreeC as needed, Preferably it is 150-700 degreeC.
[0170]
Examples of the organic carrier include granular or particulate solid organic compounds having a particle size of 10 to 300 μm. Examples of these organic compounds include (co) polymers, vinylcyclohexane, and styrene, which are mainly composed of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. (Co) polymer produced | generated as a main component can be mentioned.
[0171]
When the olefin polymerization catalyst (2) is formed from each component as described above, the contact order of the components is arbitrary, but preferably the carrier, the organoaluminum oxy compound (E-1) and / or Lewis The acid or ionic compound (E-2) (hereinafter component (E)) is mixed and contacted, then the metallocene compound (D) is mixed and contacted, and if necessary, the organoaluminum compound is mixed and contacted.
[0172]
Each of the above components can be contacted with these in a reaction-inert hydrocarbon solvent.
When the catalyst for olefin polymerization (2) is formed using a carrier, the metallocene compound (D) is 5 × 10 5 per gram of the carrier.^-6~ 5x10^-FourGram atom (transition metal atom derived from metallocene compound (D)), preferably 1 × 10^-Five~ 2x10^-FourIt is desirable to form a supported catalyst in the amount of grams atoms.
[0173]
The total amount of aluminum per gram of carrier is 10 in total of aluminum in component (E-1) and aluminum in the organoaluminum compound.^-3~ 5x10^-2Gram atoms, preferably 2 × 10^-3~ 2x10^-2It is desirable to be used in the amount of gram atoms.
[0174]
These components are usually contacted at a temperature of −50 to 150 ° C., preferably −20 to 120 ° C., for 1 minute to 50 hours, preferably 10 minutes to 25 hours to form a catalyst supported on a carrier. .
[0175]
The olefin polymerization catalyst (2) used in the present invention can also be used after prepolymerizing an olefin with the above catalyst component.
This prepolymerization can be carried out in the same manner as the prepolymerization of the olefin polymerization catalyst (1) except that the catalyst components are changed.
[0176]
As the prepolymerized olefin, those similar to the olefin used in the prepolymerization of the olefin polymerization catalyst (1) can be used, and among these, ethylene, α-olefin, etc. used in the main polymerization are preferably used. It is done.
[0177]
In the prepolymerization, it is desirable to prepolymerize the olefin as described above in an amount of 1 to 100,000 g, preferably 2 to 50000 g, per 1 g of the metallocene compound (D) to form a prepolymerization catalyst.
[0178]
The concentration of the metallocene compound (D) in the prepolymerization system is usually 1 × 10 5 per liter of polymerization volume.^-6~ 2x10^-2Mol / liter, preferably 5 × 10^-Five-10^-2It is preferably used in an amount of mol / liter.
[0179]
Component (E) is an atomic ratio (Al or B / transition metal) with the transition metal in the metallocene compound (D), and is usually used in an amount of 10 to 500, preferably 20 to 200.
[0180]
Further, the carrier is used as necessary in the amount as described above, and the organoaluminum compound preferably has an atomic ratio (Al / Al or B) to aluminum or boron in the component (E) of usually 0.03 to 3. Can be used as needed in an amount of 0.05 to 1.5.
[0181]
The prepolymerization can be carried out at a temperature of -20 to 80 ° C, preferably 0 to 60 ° C for 0.5 to 100 hours, preferably about 1 to 50 hours.
The prepolymerization can be performed in the presence of each catalyst component as described above, for example, by introducing an olefin into a polymerization-inert hydrocarbon solvent. Specifically, when using a catalyst supported on a carrier, This can be done as follows.
[0182]
Component (E) is added to the carrier suspension suspended in hydrocarbon and allowed to react for a predetermined time. The supernatant is then removed and the resulting solid component is resuspended with hydrocarbons. The metallocene compound (D) is added to the system and reacted for a predetermined time, and then the supernatant is removed to obtain a solid catalyst component. Subsequently, a prepolymerized catalyst can be obtained by adding the solid catalyst component obtained above to a hydrocarbon containing an organoaluminum compound, and introducing and polymerizing the olefin therein.
[0183]
The prepolymerization can be performed either batchwise or continuously, and can be performed under reduced pressure, normal pressure, or increased pressure. In the prepolymerization, a molecular weight regulator such as hydrogen can be used.
[0184]
The ethylene copolymer [II] used in the present invention is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst (2) or the prepolymerization catalyst as described above. It is obtained by polymerizing. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene. , 1-hexadecene, 1-octadecene, 1-eicosene and the like, and two or more of these may be used in combination. Of these, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like are preferably used.
[0185]
This copolymerization of ethylene and α-olefin can be carried out by any of gas phase polymerization, liquid polymerization such as suspension polymerization, solution polymerization, etc., and any of batch, semi-continuous and continuous This method can also be performed.
[0186]
In the suspension polymerization, a polymerization inert hydrocarbon may be used as a polymerization solvent, or olefin itself may be used as a solvent. As this hydrocarbon, polymerization-inactive hydrocarbons as shown in the prepolymerization of the olefin polymerization catalyst (1) can be used. Of these, aliphatic hydrocarbons and alicyclic hydrocarbons can be used. Oil fractions are preferably used.
[0187]
In the present invention, when a compound represented by the formula (3) is used as the metallocene compound (D), it is preferably carried out by a gas phase polymerization method or a liquid phase polymerization method, and a compound represented by the formula (4) is used. In such a case, it is preferably carried out by a solution polymerization method.
[0188]
In the polymerization system, the metallocene compound (D) or the prepolymerization catalyst is about 1 × 10 6 as the concentration of transition metal atoms per liter of polymerization volume.^-8~ 1x10^-3Gram atoms, preferably 1 × 10^-7~ 1x10^-FourIt is desirable to be used in the amount of gram atoms. Component (E) is an atomic ratio (Al or B / transition metal) with the transition metal in the metallocene compound (D), and is usually used in an amount of 10 to 500, preferably 20 to 200. The olefin polymerization catalyst (2) may be a catalyst supported on a carrier as described above.
[0189]
When a prepolymerization catalyst is used during the copolymerization of ethylene and α-olefin, the use of component (E) is optional and may or may not be used, but when adding component (E) The transition metal in the polymerization system can be used in an amount of 10 to 500, preferably 20 to 200.
[0190]
The organoaluminum compound is necessary in such an amount that the atomic ratio (Al / Al or B) to aluminum or boron in the component (E) is usually 0.03 to 3, preferably 0.05 to 1.5. Can be used accordingly.
[0191]
The copolymerization of ethylene and α-olefin is usually at a temperature of −50 to 150 ° C., preferably 0 to 120 ° C. in the liquid phase polymerization method, and usually at a temperature of 0 to 120 ° C., preferably 20 to 100 ° C. in the gas phase polymerization method. It is desirable to implement in.
[0192]
This copolymerization is usually performed at normal pressure to 100 kg / cm.²Preferably normal pressure ~ 50kg / cm²Performed under the conditions of
When ethylene and α-olefin are copolymerized using the olefin polymerization catalyst (2) as described above, a low crystalline or amorphous crystalline ethylene copolymer [II] having a narrow composition distribution is obtained. .
[0193]
The ethylene copolymer [II] obtained as described above contains units derived from ethylene in an amount of 55 to 99 mol%, preferably 65 to 98 mol%, more preferably 70 to 96 mol%,
It is desirable to contain units derived from an α-olefin having 3 to 20 carbon atoms in an amount of 1 to 45 mol%, preferably 2 to 35 mol%, more preferably 4 to 30 mol%.
[0194]
The composition of the ethylene copolymer is¹³It can be determined by C-NMR spectrum. Of ethylene copolymer¹³The C-NMR spectrum was obtained by uniformly dissolving about 200 mg of a copolymer sample in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube, measuring temperature 120 ° C., measuring frequency 25.05 MHz, spectrum width 1500 Hz, pulse repetition time 4. It can be measured under conditions of 2 sec. And a pulse width of 6 μsec.
[0195]
The density of the ethylene copolymer [II] is 0.860 to 0.940 g / cm.^ThreePreferably 0.860-0.935 g / cm^ThreeMore preferably from 0.860 to 0.930 g / cm^ThreeIt is desirable that
[0196]
The melt flow rate MFR of the ethylene copolymer [II] is from 0.01 to 500 g / 10 minutes, preferably from 0.05 to 300 g / 10 minutes.
Olefin polymer composition
The olefin polymer composition according to the present invention was produced as described above.
30 to 98% by weight of propylene-based block copolymer [I], preferably 35 to 98% by weight, more preferably 55 to 97% by weight,
The ethylene-based copolymer [II] is contained in an amount of 70 to 2% by weight, preferably 65 to 2% by weight, more preferably 45 to 3% by weight.
[0197]
In order to form an olefin polymer composition from a propylene-based block copolymer [I] and an ethylene-based copolymer [II], a method generally known as a kneading method for a resin composition [I ] And [II] can be prepared by kneading.
[0198]
At this time, for example, a kneading apparatus such as a single-screw extruder, a twin-screw extruder, a twin-screw kneader, a Banbury mixer, or a roll can be used.
The olefin polymer composition obtained as a kneaded product by kneading the above components with a kneading apparatus such as an extruder is usually used after being formed into pellets.
[0199]
Each component forming the olefin polymer composition according to the present invention is excellent in kneadability and can easily form a uniform composition olefin polymer composition.
Thus, the olefin polymer composition according to the present invention formed from the specific propylene-based block copolymer [I] and the ethylene-based copolymer [II] is excellent in both rigidity and impact strength. . For example, rigidity and impact resistance compared to an olefin polymer composition formed using an ethylene copolymer produced by using a conventionally known solid titanium catalyst component instead of the ethylene copolymer [II] Excellent strength.
[0200]
Furthermore, the olefin polymer composition according to the present invention is excellent in moldability, heat resistance and the like, and can be molded into various molded products and used in a wide range of applications.
The olefin polymer composition according to the present invention may contain other components together with the components [I] and [II] described above within a range not to impair the object of the present invention.
[0201]
Examples of such other components include thermoplastic resins and thermosetting resins, and specifically, α-olefin homopolymers such as polyethylene, polypropylene other than the above, poly 1-butene, and α-olefin. Olefin copolymer, copolymer of α-olefin and vinyl monomer, modified olefin polymer such as maleic anhydride modified polypropylene, nylon, polycarbonate, ABS, polystyrene, polyvinyl chloride, polyphenylene oxide, petroleum resin, phenol resin Etc.
[0202]
Furthermore, the olefin polymer composition according to the present invention may contain various additives. Examples of such additives include nucleating agents, heat stabilizers, phenol-based, sulfur-based, phosphorus-based antioxidants, lubricants, antistatic agents, dispersants, copper damage inhibitors, neutralizing agents, foaming agents. , Plasticizer, anti-bubble agent, flame retardant, crosslinking agent, peroxide flow improver, UV absorber, light stabilizer, weather stabilizer, weld strength improver, slip agent, anti-blocking agent, anti-fogging Agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, fillers, rubber components, and the like.
[0203]
【The invention's effect】
As described above, the olefin polymer composition according to the present invention is formed from a specific propylene-based block copolymer [I] and an ethylene-based copolymer [II].
[0204]
The propylene-based block copolymer [I] has a highly stereoregular polypropylene component and a rubber component, and the ethylene-based copolymer [II] has a narrow composition distribution. Such an olefin polymer composition according to the present invention is excellent in mechanical strength such as rigidity and also in impact resistance strength.
[0205]
【Example】
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
[0206]
[Example 1]
Production of propylene-based block copolymer [I] -1
[Preparation of solid titanium catalyst component (A)]
An anhydrous magnesium chloride (95.2 g), decane (442 ml) and 2-ethylhexyl alcohol (390.6 g) were heated at 130 ° C. for 2 hours to form a homogeneous solution, and then 21.3 g of phthalic anhydride was added to the solution. Stir and mix at 1 ° C. for 1 hour to dissolve phthalic anhydride.
[0207]
The homogeneous solution thus obtained was cooled to room temperature, and then 75 ml of this homogeneous solution was added dropwise over 1 hour into 200 ml of titanium tetrachloride maintained at -20 ° C. After charging, the temperature of the mixture was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added and stirred at the same temperature for 2 hours. Retained.
[0208]
After completion of the reaction for 2 hours, the solid part was collected by hot filtration, and the solid part was resuspended in 275 ml of titanium tetrachloride and then heated again at 110 ° C. for 2 hours.
After completion of the reaction, the solid part was again collected by hot filtration, and washed thoroughly with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.
[0209]
The solid titanium catalyst component (A) prepared as described above was stored as a decane slurry, and a part thereof was dried for the purpose of examining the catalyst composition.
The composition of the solid titanium catalyst component (A) thus obtained was 2.3% by weight of titanium, 61% by weight of chlorine, 19% by weight of magnesium, and 12.5% by weight of DIBP.
[0210]
[Preliminary polymerization]
In a 400 ml four-necked glass reactor equipped with a stirrer, under a nitrogen atmosphere, 100 ml of purified hexane, 10 mmol of triethylaluminum, 2 mmol of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane (IPAMP) and the above. After adding 1 mmol of the solid titanium catalyst component (A) thus obtained in terms of titanium atom, propylene was fed to the reactor at a rate of 3.2 N liter / hour for 1 hour. The polymerization temperature was kept at 20 ° C.
[0211]
When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, and the washing operation including removal of the supernatant and addition of purified hexane was performed twice, and then the suspension was resuspended in purified hexane and transferred to the catalyst bottle. Thus, a prepolymerized catalyst (a) was obtained.
[0212]
[Polymerization]
An autoclave with an internal volume of 17 liters was charged with 3 kg of propylene and 45 liters of hydrogen, and the temperature was raised to 60 ° C. a) was charged at 0.05 mmol in terms of titanium atoms. After raising the temperature to 70 ° C., this was held for 40 minutes to carry out homopolymerization of propylene.
[0213]
After completion of the homopolymerization of propylene, the vent valve was opened and the pressure was released until the internal pressure of the polymerization reactor reached normal pressure.
After completion of the depressurization, ethylene and propylene were subsequently copolymerized. That is, ethylene was supplied to the polymerization vessel in amounts of 240 N liter / hour, propylene 960 N liter / hour, and hydrogen 10 N liter / hour. The pressure in the polymerization vessel is 10 kg / cm²The vent opening of the polymerization vessel was adjusted so as to be G. The temperature was kept at 70 ° C. and polymerization was carried out for 50 minutes. The polymerization reaction is stopped by adding a small amount of ethanol, the unreacted gas in the polymerization vessel is purged, and the resulting white powder is dried at 80 ° C. under reduced pressure, and the following polymer (propylene block copolymer) Compound [I] -1) was obtained. The yield was 1820g.
[0214]
MFR; 52 g / 10 minutes,
Bulk specific gravity: 0.45 g / ml,
Decane-soluble component content: 9.1 wt% (Intrinsic viscosity [η]; 2.3 dl / g, ethylene unit content; 37.0 mol%)
Decane-insoluble component (ethylene unit content; 0.8 mol%, boiling heptane-insoluble component content; 94.4% by weight)
Ethylene copolymer [ II ]Manufacturing of
Using a 2 liter continuous polymerization reactor, purified toluene is 2 liter / hr, methylaluminoxane is 10 mmol / hr in terms of aluminum atom, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride is zirconium atom Continuously fed at a rate of 0.002 mmol / hr in terms of conversion, and continuously fed at a rate of 360 liters / hr of ethylene and 240 liters / hr of 1-butene at the same time in the polymerization vessel. Polymerization was performed below. The produced polymer solution was continuously withdrawn from the polymerization vessel, the polymerization was stopped by adding a small amount of methanol, the polymer solution was further transferred into a large amount of methanol, and the precipitated polymer was dried under reduced pressure at 130 ° C. for 12 hours. .
[0215]
As described above, an ethylene copolymer [II] was obtained in an amount of 70 kg / hr.
The density of the ethylene copolymer [II] is 0.887 g / cm.^ThreeAnd the MFR was 7.1 g / 10 min.
[0216]
Olefin polymer composition
80% by weight of the propylene-based block copolymer [I] -1 obtained as described above and 20% by weight of the ethylene-based copolymer [II] are mixed, and further, with respect to 100 parts by weight of the mixture. , Tetrakis (methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate) methane 0.05 parts by weight, tris (mixed mono & dinonylphenyl phosphite) 0.05 parts by weight and calcium stearate 0 .1 part by weight was added and mixed, and a granulated product of an olefin polymer composition was obtained by kneading and granulating at 250 ° C. using an extrusion granulator (manufactured by Thermoplastic) having a screw diameter of 20 mm. .
[0217]
The melt flow rate MFR (ASTM D1238: 230 ° C., under 2.16 kg load) of the obtained olefin polymer composition is shown in Table 1.
From the obtained granulated material, the following ASTM standard test pieces are prepared at a molding temperature of 200 ° C. using an injection molding machine (manufactured by TOSHIBA MACHINE), and the flexural modulus (in accordance with the ASTM standard measurement method) FM) and Izod impact strength (IZ) were measured.
[0218]
Flexural modulus (FM): Measured according to ASTM-D790.
Test piece 12.7cm × 12.7mm × 3.0mm
Izod impact strength (IZ): Measured according to ASTM-D256.
[0219]
Test piece 12.7cm x 12.7mm x 6.0mm (rear notch)
The results are shown in Table 1.
[0220]
[Example 2]
In Example 1, an olefin polymer composition was used in the same manner as in Example 1 except that 75% by weight of propylene-based block copolymer [I] -1 and 25% by weight of ethylene-based copolymer [II] were used. Got.
[0221]
The results are shown in Table 1.
[0222]
[Example 3]
A propylene-based block copolymer [I] -2 was obtained in the same manner as in Example 1 except that the “polymerization” was performed as follows in Example 1. An olefin polymer composition was obtained in the same manner as in Example 1 except that this propylene-based block copolymer [I] -2 was used in place of the propylene-based block copolymer [I] -1.
[0223]
The results are shown in Table 1.
[Polymerization]
An autoclave with an internal volume of 17 liters was charged with 3 kg of propylene and 45 liters of hydrogen, heated to 60 ° C., 15 mmol of triethylaluminum, 15 mmol of dicyclopentyldimethoxysilane (DCPMS) and the prepolymerization obtained in Example 1. Catalyst (a) was charged at 0.05 mmol in terms of titanium atom. After raising the temperature to 70 ° C., this was held for 40 minutes to carry out homopolymerization of propylene.
[0224]
After completion of the homopolymerization of propylene, the vent valve was opened and the pressure was released until the internal pressure of the polymerization reactor reached normal pressure.
After completion of the depressurization, ethylene and propylene were subsequently copolymerized. That is, ethylene was supplied to the polymerization vessel in an amount of 240 N liter / hour and propylene in an amount of 960 N liter / hour. The pressure in the polymerization vessel is 10 kg / cm²The vent opening of the polymerization vessel was adjusted so as to be G. The temperature was kept at 70 ° C. and polymerization was carried out for 80 minutes. The polymerization reaction is stopped by adding a small amount of ethanol, the unreacted gas in the polymerization vessel is purged, and the resulting white powder is dried at 80 ° C. under reduced pressure, and the following polymer (propylene block copolymer) Combined [I] -2) was obtained. The yield was 1735g.
[0225]
MFR; 50 g / 10 minutes,
Bulk specific gravity: 0.45 g / ml,
Decane-soluble component content: 8.4 wt% (Intrinsic viscosity [η]; 6.6 dl / g, ethylene unit content; 40.1 mol%)
Decane-insoluble component (ethylene unit content; 0.8 mol%, boiling heptane-insoluble component content; 94.5% by weight)
[0226]
[Example 4]
In Example 3, an olefin polymer composition was used in the same manner as in Example 1 except that 75% by weight of propylene-based block copolymer [I] -2 and 25% by weight of ethylene-based copolymer [II] were used. Got.
[0227]
The results are shown in Table 1.
[0228]
[Table 1]

Claims (1)

[I] (A) Solid titanium catalyst component containing magnesium, titanium, halogen and polyvalent carboxylic acid ester,
(B) an organometallic compound, and (C) 1, at least one electron donor comprising a member selected from 3-diethers, at least one or is selected from dimethoxy compound represented by the following formula (ii) and 1 , 3 -Diethers comprising at least one electron donor
Wherein R ^a and R ^c are each independently a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or a carbon adjacent to Si. Represents a hydrocarbon group in which secondary carbon or tertiary carbon is present.)
In the presence of an olefin polymerization catalyst (1) consisting of
[I-1] a step of producing a crystalline polypropylene component by homopolymerizing propylene or copolymerizing propylene and another α-olefin;
[I-2] A step of producing a low-crystalline or non-crystalline ethylene / propylene copolymer component by copolymerizing ethylene and propylene in any order to produce a propylene-based block copolymer With manufacturing,
[II] (D) a transition metal compound containing a ligand having a cyclopentadienyl skeleton,
And (E) (E-1) an organoaluminum oxy compound, and / or
(E-2) In the presence of an olefin polymerization catalyst (2) comprising a Lewis acid or an ionic compound,
Ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized to produce a low crystalline or non-crystalline ethylene copolymer,
Next, the propylene block copolymer and the low crystalline or non-crystalline ethylene copolymer are kneaded, and 30 to 98 parts by weight of the propylene block copolymer, and the low crystalline or A method for producing an olefin polymer composition, comprising preparing a composition comprising 70 to 2 parts by weight of an amorphous ethylene copolymer.