JP3401306B2 - Propylene polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a triad tacticity city.
High propylene-based polymer
You. [0002] BACKGROUND OF THE INVENTION Propylene polymers, especially homopoly
Propylene is rigid, surface hardness, heat resistant, glossy, transparent
Excellent industrial properties, various industrial parts, containers,
It is used for various applications such as rubber and nonwoven fabric. However, conventional propylene-based polymers
Depends on the application, transparency, impact strength, etc.
It was not enough. For this reason, rigidity, heat resistance, surface hardness
Excellent in degree and gloss, excellent in transparency and impact resistance
There is a demand for the appearance of a propylene-based polymer. [0004] The present inventors have studied in view of such a situation.
As a result, the propylene chain consisting of the head-tail bond¹³C
-High triad tacticity measured by NMR,
And the position irregular units are in a specific proportion and
Propylene polymer has high transparency and impact resistance
Complete the present invention by finding superior properties such as strength
I came to. [0005] SUMMARY OF THE INVENTION The present invention provides a triad tacticity
With the aim of providing a high novel propylene polymer
are doing. [0006] SUMMARY OF THE INVENTION The propylene polymer according to the present invention comprises: (A) a propylene unit chain comprising a head-tail bond,¹³
Triad tacticity measured by C-NMR (Poly
Of any three propylene units in the mer chain
The direction of the methyl branch in the
3 chains of propylene units in which the len units are linked head-to-tail
Percentage)Is 90.0% or more, (B)¹³During the total propylene insertion, measured by C-NMR
Positionally irregular units based on 2,1-insertion of propylene monomer
Is 0.7~ 2.0%And propylene monomer
Of the irregular units based on the 1,3-insertion of0.03%
Is the following, (C) the intrinsic viscosity measured in decalin at 135 ° C.1~
It is characterized by being in the range of 12 dl / g. [0007] DETAILED DESCRIPTION OF THE INVENTION The propylene-based polymerization of the present invention is described below.
The body will be described specifically. The propylene-based weight of the present invention
Coalescence is a polymer consisting of propylene units, and is preferably
Or homopolypropylene, but other than propylene.
Less than 0.5 mol% of structural units derived from refining
Preferably less than 0.3 mol%, more preferably 0.1 mole
%. The propylene polymer of the present invention has a head-to-tail
Propylene unit chain consisting of¹³Measured by C-NMR
Triad tacticity (any in the polymer chain)
Of the three propylene units
The direction of the chill branch is the same, and each propylene unit is head-
The proportion of three propylene units linked at the tail) is 90
% Or more, preferably 93% or more, more preferably 95%
It is desirable that this is the case. In addition, triad tactics
The tee is hereinafter referred to as a mm fraction. [0009]¹³The C-NMR spectrum is shown for samples 50 to 6
0 mg in an NMR sample tube (5 mmφ)
Lobutadiene, o-dichlorobenzene or 1,2,4-tric
Lorobenzene about 0.5ml to about 0.05ml lock solvent
Completely dissolved in a solvent containing deuterated benzene
And measure at 120 ° C by proton complete decoupling method.
Specified. Measurement conditions are flip angle 45 °, pulse
3.4T interval₁(T₁Means the spin lattice relaxation of the methyl group
(The longest value of the sum time) is selected. Propylene polymerization
Of the methylene and methine groups in the₁Is methyl
Group, the magnetization of all the carbons
Recovery is more than 99%. The chemical shift is caused by the head-to-tail bond,
Third unit of 5 propylene units with the same branch direction
The methyl group of the eye was set as 21.593 ppm,
The chemical shift of the peak was based on this. This criterion
Then, 3 chains of propylene units represented by PPP (mm)
The peak based on the methyl group of the second unit in the figure is 21.1-2.1.
Propylene represented by PPP (mr) is in the range of 21.8 ppm.
Peak based on the methyl group of the second unit of the 3 units of the ren unit
Is in the range of 20.2 to 21.1 ppm, and PPP (rr)
The methyl of the second unit of the three chains of propylene units represented by
Group-based peaks appear between 19.4 and 20.2 ppm
You. Here, PPP (mm) and PPP (m
r) and PPP (rr) are [0012] Embedded image A head-to-tail binding propyle represented by
This shows three units per unit. Further, the propylene according to the present invention
The system polymer includes these PPP (mm), PPP (mr),
And 2,1-insertion in addition to the rule structure represented by PPP and (rr)
Including the irregular units based on the
It has a small amount of the partial structures (i) and (ii). [0014] Embedded image Among the irregular structures, A, B, C, and
The carbon of D does not meet the definition of the mm fraction described above. A,
B carbon is in the range of 16.5 to 17.5 ppm, and C carbon is 2
At around 0.8 ppm (mr region), and D carbon is 20.
Resonates around 7 ppm (mr region) (however, the structure (i)
And confirmation of structure (ii) not only for these methyl groups,
Confirm peaks of adjacent methylene and methine groups and combine them
Need to do this). Further, in the partial structure (ii), hydrogen transfer polymerization
Results in-(CH_Two)_Four-Units are formed, one methyl group phase
For the time being has disappeared. Therefore, in the entire polymer chain
The mm fraction can be expressed by the following equation. [0017] (Equation 1) In this equation, ΣICH_ThreeIs the total methyl group
Indicates the area. Iαδ and Iβγ are αβ
Area of peak (resonating around 37.1 ppm), βγ peak
(Resonance around 27.3 ppm). Note that these
The nomenclature of the methylene peak was determined by the method of Carman et al. (Rubber Che
m. Technol.,44(1971), 781). During the polymerization of the propylene-based polymer,
1,2-insertion of len monomer (methylene side is bonded to catalyst)
However, in rare cases, 2,1-insertion or 1,3-insertion may occur.
You. The monomer formed by the 2,1-insertion is in the polymer chain
In the position irregular unit represented by the partial structure (i)
Form. 2,1-propylene model for total propylene insertion
Nomer insertion frequency was calculated by the following equation. [0020] (Equation 2) Similarly, for the total propylene insertion,
Insertion of 1,3-propylene monomer represented by partial structure (ii)
The frequency was calculated by the following equation. [0022] (Equation 3) The propylene polymer according to the present invention comprises:¹³C
-2,1-insertion in total propylene insertion measured by NMR
Based on the position of irregular units is 0.7% or more, preferably
Is desirably 0.7 to 2.0%. In addition,
Ming propylene-based polymer is 1,3-
0.05% or less of the position irregular unit based on insertion,
Preferably 0.04% or less, more preferably 0.03% or less
It is preferably below. The propylene polymer of the present invention has a viscosity of 135
C., intrinsic viscosity [η] measured in decalin is 0.1 to 1
2 dl / g, preferably 0.5 to 12 dl / g, more preferably
More preferably, it is in the range of 1 to 12 dl / g.
No. The propylene polymer of the present invention
If (A) a transition metal compound as described below; (B) (B-1) an organic aluminum oxy compound, and (B-2) reacting with the transition metal compound (A) to form an ion pair
At least one selected from the group consisting of forming compounds
And optionally (C) Olefin polymerization comprising an organoaluminum compound
Polymerizes propylene in the presence of a catalyst for
To copolymerize propylene and a small amount of α-olefin
You can get more. Hereinafter, the production of the propylene polymer of the present invention will be described.
The catalyst for olefin polymerization used for is described.
Transition forming olefin polymerization catalyst used in the present invention
Metal compound (A) (hereinafter referred to as “component (A)”)
There is. ) Is a transition metallization represented by the following general formula (I).
It is a compound. [0027] Embedded image In the formula, M represents a group IVa, Va or VIa of the periodic table.
Transition metals, specifically, titanium, zirconium
Um, Hafnium, Vanadium, Niobium, Tantalum, Qu
Rom, molybdenum, and tungsten, preferably
Titanium, zirconium and hafnium, especially preferred
Or zirconium. R¹And R^TwoIs a hydrogen atom, a halogen atom,
C1-C20 hydrocarbon group, C1-C20 halogen
Hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing
Shows an organic group, a nitrogen-containing group or a phosphorus-containing group.
Is a halogen atom such as fluorine, chlorine, bromine and iodine;
Methyl, ethyl, propyl, butyl, hexyl, cyclo
Hexyl, octyl, nonyl, dodecyl, eicosyl,
Alkyl groups such as norbornyl and adamantyl, vinyl
Alkenyl such as phenyl, propenyl and cyclohexenyl
Group, benzyl, phenylethyl, phenylpropyl, etc.
Arylalkyl group, phenyl, tolyl, dimethyl
Phenyl, trimethylphenyl, ethylphenyl, propyl
Ruphenyl, biphenyl, naphthyl, methylnaphthyl,
Aryl groups such as anthracenyl and phenanthryl
A hydrocarbon group having 1 to 20 carbon atoms;
Halogenated hydrocarbon group substituted by a gen atom; methylsilyl
Mono-substituted silyls such as phenylsilyl
Dihydrocarbon substitution such as methylsilyl and diphenylsilyl
Silyl, trimethylsilyl, triethylsilyl, trip
Lopirsilyl, tricyclohexylsilyl, triphenyl
Lucilyl, dimethylphenylsilyl, methyldiphenyl
Such as silyl, tritolylsilyl, and trinaphthylsilyl
Trihydrocarbon-substituted silyl, trimethylsilyl ether
Which hydrocarbon substituted silyl silyl ether, trimethyl
Silicon-substituted alkyl groups such as silylmethyl, trimethyl
Silicon-containing aryl groups such as phenyl;
Substituents: hydroxy, methoxy, ethoxy, pro
Alkoxy groups such as oxy and butoxy, phenoxy,
Tilphenoxy, dimethylphenoxy, naphthoxy, etc.
Allyloxy group, phenylmethoxy, phenylethoxy
An oxygen-containing substituent such as an arylalkoxy group;
Sulfur content in which oxygen of the oxygenated compound is replaced by sulfur
Group; amino group, methylamino, dimethylamino, diethyl
Ruamino, dipropylamino, dibutylamino, dicycl
Alkylamino groups such as rohexylamino, phenyla
Mino, diphenylamino, ditolylamino, dinaphthyl
Arylamino groups such as amino and methylphenylamino
Or a nitrogen-containing group such as an alkylarylamino group;
Files such as methylphosphino and diphenylphosphino
And phosphorus-containing groups such as phosphino groups. Of these, R¹Is a hydrocarbon group
Is preferable, and particularly, methyl, ethyl and propyl having 1 carbon atom
It is preferably from 3 to 3 hydrocarbon groups. Also R^TwoIs water
Preferably a hydrogen atom or a hydrocarbon group, particularly a hydrogen atom
It is preferably a child. R^ThreeRepresents an alkyl group having 2 to 20 carbon atoms
Then R^FourRepresents an alkyl group having 1 to 20 carbon atoms. R^ThreeIs 2
It is preferably a tertiary or tertiary alkyl group. Also,
R^Three, R ^FourThe alkyl group represented by is a halogen atom, silicon
Halogen atom, silicon
R-containing groups include R¹, R^TwoExamples of the substituents exemplified in
Can be R^FourAre ethyl, n-propyl, i-propyl
Ropyl, n-butyl, i-butyl, sec-butyl, tert-butyl
, Pentyl, hexyl, cyclohexyl, heptyl,
Octyl, nonyl, dodecyl, aikosyl, norborny
And adamantyl, etc.
Kill group: benzyl, phenylethyl, phenylpropy
And arylalkyl groups such as tolylmethyl.
And may contain a double bond or a triple bond. R^ThreeInclude methyl and R^FourExemplified in
And an alkyl group. X¹And X^TwoIs a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
To 20 halogenated hydrocarbon groups, oxygen-containing groups or
C) represents a group containing R,¹And R^TwoSame as
Halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, carbon atoms
Examples are halogenated hydrocarbon groups of formulas 1 to 20 and oxygen-containing groups.
it can. Examples of the sulfur-containing group include the aforementioned R¹, R^TwoWhen
Similar groups, and methylsulfonate, trifluoromethyl
Tansulfonate, phenylsulfonate, benzene
Lusulfonate, p-toluenesulfonate, trime
Tylbenzenesulfonate, triisobutylbenzene
Sulfonate, p-chlorobenzene sulfonate,
Sulfones such as n-fluorobenzenesulfonate
Phosphate group, methyl sulfinate, phenyl sulfinate
G, benzene sulfinate, p-toluene sulfinate
G, trimethylbenzenesulfinate, pentafluo
Examples of sulfinate groups such as robenzenesulfinate
it can. Y is a divalent hydrocarbon having 1 to 20 carbon atoms
A divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, 2
Divalent silicon-containing group, divalent germanium-containing group, divalent
Tin-containing group, -O-, -CO-, -S-, -SO-,-
SO_Two-, -NR^Five-, -P (R^Five)-, -P (O) (R
^Five)-, -BR^Five-Or -AlR^Five-[However, R^Five
Is a hydrogen atom, a halogen atom, a hydrocarbon having 1 to 20 carbon atoms
A halogenated hydrocarbon group having 1 to 20 carbon atoms].
Specifically, methylene, dimethylmethylene, 1,2-ethylene
Dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-
Tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexane
Alkylene groups such as xylene, diphenylmethylene,
Arylalkylene groups such as phenyl-1,2-ethylene
Any divalent hydrocarbon group having 1 to 20 carbon atoms; chloromethyle
Divalent hydrocarbon groups having 1 to 20 carbon atoms such as
Genated halogenated hydrocarbon groups; methylsilylene, di
Methylsilylene, diethylsilylene, di (n-propyl)
Silylene, di (i-propyl) silylene, di (cyclohexyl)
Sil) silylene, methylphenylsilylene, diphenyl
Silylene, di (p-tolyl) silylene, di (p-chlorophene)
Nyl) alkylsilylenes such as silylene, alkylants
Ylsilylene, arylsilylene group, tetramethyl-1,2
-Disilyl, tetraphenyl-1,2-disilyl, etc.
Kildisilyl, alkylaryldisilyl, arylsi
A divalent silicon-containing group such as a lyl group;
Bivalent germanium in which organic silicon is replaced by germanium
-Containing group; silicon of the above divalent silicon-containing group is converted to tin
A substituted divalent tin-containing substituent, and the like;^FiveIs
The R¹, R^TwoThe same halogen atom as above, having 1 to 20 carbon atoms
Hydrocarbon group, halogenated hydrocarbon group having 1 to 20 carbon atoms
It is. Of these, divalent silicon-containing groups, divalent gels
Preferably, it is a manium-containing group or a divalent tin-containing group.
And further preferably a divalent silicon-containing group,
Of these, alkyl silylene and alkyl aryl sil
Preferably, they are ren and arylsilylene. The transition gold represented by the above general formula (I)
The specific example of a genus compound is shown. rac-dimethylsilyl-bis (2,7-dimethyl-4-ethyl-1-
Indenyl) zirconium dichloride, rac-dimethyl
Lil-bis (2,7-dimethyl-4-n-propyl-1-indenyl
G) zirconium dichloride, rac-dimethylsilyl-bi
(2,7-dimethyl-4-i-propyl-1-indenyl) zirco
Dichloride, rac-dimethylsilyl-bis (2,7-di
Methyl-4-n-butyl-1-indenyl) zirconium dichloro
Lido, rac-dimethylsilyl-bis (2,7-dimethyl-4-sec-
Butyl-1-indenyl) zirconium dichloride, rac-
Dimethylsilyl-bis (2,7-dimethyl-4-t-butyl-1-i
Ndenyl) zirconium dichloride, rac-dimethylsilyl
Ru-bis (2,7-dimethyl-4-n-pentyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilyl-bis
(2,7-dimethyl-4-n-hexyl-1-indenyl) zirconi
Um dichloride, rac-dimethylsilyl-bis (2,7-dimethyl
Tyl-4-cyclohexyl-1-indenyl) zirconiumdi
Chloride, rac-dimethylsilyl-bis (2,7-dimethyl-4-
Methylcyclohexyl-1-indenyl) zirconiumdi
Chloride, rac-dimethylsilyl-bis (2,7-dimethyl-4-
Phenylethyl-1-indenyl) zirconium dichloride
, Rac-dimethylsilyl-bis (2,7-dimethyl-4-phenyl
Rudichloromethyl-1-indenyl) zirconium dichloro
Lido, rac-dimethylsilyl-bis (2,7-dimethyl-4-chloro
1-indenyl) zirconium dichloride, rac
-Dimethylsilyl-bis (2,7-dimethyl-4-trimethylsi
Rylmethyl-1-indenyl) zirconium dichloride, r
ac-dimethylsilyl-bis (2,7-dimethyl-4-trimethyl
Siloxymethyl-1-indenyl) zirconium dichloride
, Rac-diethylsilyl-bis (2,7-dimethyl-4-i-pro
Pyr-1-indenyl) zirconium dichloride, rac-di
(I-propyl) silylbis (2,7-dimethyl-4-i-propyl
Ru-1-indenyl) zirconium dichloride, rac-di (n
-Butyl) silylbis (2,7-dimethyl-4-i-propyl-1-
Indenyl) zirconium dichloride, rac-di (cyclo
Hexyl) silylbis (2,7-dimethyl-4-i-propyl-1-
Indenyl) zirconium dichloride, rac-methylphen
Nylsilylbis (2,7-dimethyl-4-i-propyl-1-indene
Nyl) zirconium dichloride, rac-methylphenylsi
Lilbis (2,7-dimethyl-4-t-butyl-1-indenyl) di
Ruconium dichloride, rac-diphenylsilylbis (2,
7-dimethyl-4-t-butyl-1-indenyl) zirconiumdi
Chloride, rac-diphenylsilylbis (2,7-dimethyl-4
-i-propyl-1-indenyl) zirconium dichloride,
rac-diphenylsilylbis (2,7-dimethyl-4-ethyl-1-
Indenyl) zirconium dichloride, rac-di (p-tri
) Silylbis (2,7-dimethyl-4-i-propyl-1-indene)
Nil) zirconium dichloride, rac-di (p-chlorophen
Nyl) silylbis (2,7-dimethyl-4-i-propyl-1-yne
Denenyl) zirconium dichloride, rac-dimethylsilyl
Bis (2-methyl-4-i-propyl-7-ethyl-1-indene
B) Zirconium dibromide rac-dimethylsilyl-bis (2,7-dimethyl-4-i-propyl
1-indenyl) zirconium dimethyl, rac-dimethyl
Lil-bis (2,7-dimethyl-4-i-propyl-1-indenyl)
Zirconium methyl chloride, rac-dimethylsilyl-bi
(2,7-dimethyl-4-i-propyl-1-indenyl) zirco
Nium-bis (trifluoromethanesulfonato), rac-
Dimethylsilyl-bis (2,7-dimethyl-4-i-propyl-1-
Indenyl) zirconium-bis (p-phenylsulfina
G), rac-dimethylsilyl-bis (2-ethyl-4-i-propyl
Ru-7-methyl-1-indenyl) zirconium dichloride, r
ac-dimethylsilyl-bis (2-phenyl-4-i-propyl-7-
Methyl-1-indenyl) zirconium dichloride and the like. Of these, i-propyl and sec-butyl
With branched alkyl groups such as tyl and tert-butyl groups
Is particularly preferred. In the present invention, the compounds as described above
Zirconium metal is replaced by titanium metal, hafnium
Metal, vanadium metal, niobium metal, tantalum metal,
Replaced by rom metal, molybdenum metal, tungsten metal
The obtained transition metal compound can also be used. The transition metal compound is usually in a racemic form.
Used as a catalyst component for olefin polymerization.
Alternatively, an S type can be used. Used in the present invention
(B-1) Organo-aluminium forming catalyst for olefin polymerization
Muoxy compound (hereinafter referred to as “component (B-1)”).
is there. ) May be a conventionally known aluminoxane.
And is exemplified in JP-A-2-78687.
Such as benzene-insoluble organoaluminum oxy compounds
It may be. Conventionally known aluminoxanes include, for example,
It can be manufactured by the method as described above. (1) Compounds containing adsorbed water or containing water of crystallization
Salts such as magnesium chloride hydrate, copper sulfate hydrate
Material, aluminum sulfate hydrate, nickel sulfate hydrate, salt
To a suspension of a hydrocarbon medium such as cerium iodide hydrate
Organoaluminum compounds such as lithium alkyl aluminum
A method of adding and reacting. (2) benzene, toluene, ethyl ether, tetrahi
Trialkyl aluminum in a medium such as drofuran
Water, ice, and water vapor directly to organic aluminum compounds such as
How to make it work. (3) Tris in media such as decane, benzene, toluene
Organoaluminum compounds such as alkylaluminum
Dimethyl tin oxide, dibutyl tin oxide, etc.
To react the organic tin oxide. The aluminoxane is used in a small amount of organic gold.
A genus component may be contained. The above aluminum that was recovered
Solvent or unreacted organic aluminum from noxane solution
After distilling off the compound, it is redissolved in a solvent or
It may be suspended in a poor solvent of aluminoxane. Used in preparing aluminoxane
As the organic aluminum compound, specifically,
Chill aluminum, triethyl aluminum, tripro
Pill aluminum, triisopropyl aluminum,
N-butylaluminum, triisobutylaluminum
System, tri-sec-butylaluminum, tri-tert-butyla
Luminium, tripentyl aluminum, trihexyl
Aluminum, trioctyl aluminum, tridecyl
Trialkyl aluminum such as aluminum;
Clohexyl aluminum, tricyclooctyl aluminum
Tricycloalkylaluminum, such as aluminum; dimethyl
Aluminum chloride, diethylaluminum chloride
, Diethyl aluminum bromide, diisobutyl aldehyde
Dialkyl aluminum halide such as minium chloride
De; diethyl aluminum hydride, diisobutyl
Dialkylaluminum such as aluminum hydride
Muhydride; dimethyl aluminum methoxide, di
Dialkyl aluminum such as ethyl aluminum ethoxide
Alkoxide; diethylaluminum phenoxy
Dialkyl aluminum aryloxides such as
No. Of these, trialkylaluminum
And tricycloalkylaluminum are preferred.
Methyl aluminum is particularly preferred. In addition, aluminum tree
Organoaluminum compounds used in preparing sun
Is an isoprenyl alkenyl represented by the following general formula (II)
Minium can also be used. [0044] (I-C_FourH₉)_xAl_y(C_FiveH_Ten)_z    … (II) (Where x, y, and z are positive numbers, and z ≧ 2x
You. ) The above-mentioned organoaluminum compound is used alone
Alternatively, they are used in combination. Used for aluminoxane solution or suspension
The solvents used are benzene, toluene, xylene,
Aromatic hydrocarbons such as cumene and cymene, pentane and hex
Sun, heptane, octane, decane, dodecane, hexa
Aliphatic hydrocarbons such as decane and octadecane, cyclope
Pentane, cyclohexane, cyclooctane, methylcycl
Alicyclic hydrocarbons such as lopentane, gasoline, kerosene, light
Petroleum fractions such as oil or the above aromatic hydrocarbons and aliphatics
Hydrocarbons, halides of alicyclic hydrocarbons, especially salts
Hydrocarbon solvents such as iodides and bromides are exemplified. So
And ethers such as ethyl ether and tetrahydrofuran
Ters can also be used. Of these solvents,
Aromatic or aliphatic hydrocarbons are preferred. Olefin polymerization catalyst used in the present invention
(B-2) reacting with the transition metal compound (A)
Compound forming an ion pair (hereinafter referred to as “component (B-2)”)
Sometimes. ) Is described in JP-A-1-501950.
Japanese Patent Application Laid-Open No. Hei.
JP 79005, JP-A-3-179006,
JP-A-3-207703, JP-A-3-207704
No. 5,547,718, etc.
Isocyanic acid, ionic compounds and carborane compounds
Can be As the Lewis acid, triphenylboron,
Tris (4-fluorophenyl) boron, Tris (p-tri
Le) boron, tris (o-tolyl) boron, tris (3,5-
Dimethylphenyl) boron, tris (pentafluorop)
Enyl) boron, MgCl_Two, Al_TwoO_Three, SiO_Two-Al_Two
O_ThreeAnd the like. As the ionic compound, triphenylca
Rubenium tetrakis (pentafluorophenyl) bore
, Tri-n-butylammonium tetrakis (pentaf
Fluorophenyl) borate, N, N-dimethylanilinium
Tetrakis (pentafluorophenyl) borate, Fe
Rosenium tetra (pentafluorophenyl) borate
And the like. As the carborane compound, dodecabora
, 1-carboundecaborane, bis-n-butylammonium
(1-carbedodeca) borate, tri-n-butyl ammonium
(7,8-dicarbaundeca) borate, tri-n-butyl
Ammonium (Trideca hydride-7-carbounde)
F) borate and the like. The transition metal compound (A) as described above and
Two or more compounds (B-2) that form an ion pair upon reaction
They can be used in combination. I used in the present invention
(C) Organoalumination to form fin polymerization catalyst
Compound (hereinafter sometimes referred to as “component (C)”).
For example, an organic alcohol represented by the following general formula (III)
A minium compound can be exemplified. R⁹ _nAlX_3-n  … (III) (Where R⁹Is a hydrocarbon group having 1 to 12 carbon atoms, and X
Is a halogen atom or a hydrogen atom, and n is 1 to 3.
You. ) In the general formula (III), R⁹Has 1 to 1 carbon atoms
12 hydrocarbon groups such as alkyl groups and cycloalkyl groups
Or an aryl group, specifically, a methyl group,
Tyl group, n-propyl group, isopropyl group, isobutyl
Group, pentyl group, hexyl group, octyl group, cyclopen
Tyl group, cyclohexyl group, phenyl group, tolyl group, etc.
It is. Such an organoaluminum compound (C)
Specific examples include the following compounds
You. Trimethyl aluminum, triethyl aluminum
System, triisopropylaluminum, triisobutyla
Luminium, trioctyl aluminum, tri (2-ethyl
Lehexyl) aluminum, tridecyl aluminum, etc.
Which trialkyl aluminum; isoprenyl aluminum
Alkenyl aluminum such as aluminum; dimethyl aluminum
Um chloride, diethylaluminum chloride, diiso
Propyl aluminum chloride, diisobutylaluminum
Dichloride such as um chloride and dimethyl aluminum bromide
Alkyl aluminum halide; methyl aluminum chloride
Sukichloride, ethyl aluminum sesquichloride, i
Sopropyl aluminum sesquichloride, butyl aluminum
Sesquichloride, ethyl aluminum sesquibro
Alkyl aluminum sesquihalides such as amides;
Aluminum dichloride, ethyl aluminum dichloride
Lido, isopropyl aluminum dichloride, ethyl alcohol
Alkyl aluminum dihaides such as luminium dibromide
Ride; diethyl aluminum hydride, diisobu
Alkyl aluminum such as chilled aluminum hydride
Um hydride and the like. Further, an organoaluminum compound (C)
It is also possible to use a compound represented by the following general formula (IV).
it can. R⁹ _nAlL_3-n  … (IV) (Where R⁹Is the same as above, and L is -OR^TenGroup,-
OSiR¹¹ _ThreeGroup, -OAlR¹² _TwoGroup, -NR¹³ _TwoGroup, -Si
R¹⁴ _ThreeGroup or -N (R^Fifteen) AlR¹⁶ _TwoAnd n is 1 to
2 and R^Ten, R¹¹, R¹²And R¹⁶Is a methyl group, d
Tyl, isopropyl, isobutyl, cyclohexyl
R, phenyl, etc .;¹³Is a hydrogen atom, methyl
Group, ethyl group, isopropyl group, phenyl group, trimethyl
A rusilyl group or the like;¹⁴And R^FifteenIs a methyl group,
And an ethyl group. ) Such organoaluminization
In the compound, R⁷ _nAl (OALR^Ten _Two)_3-nRepresented by
Compounds such as Et_TwoAlOAlEt_Two, (Iso-Bu)_TwoAlO
Al (iso-Bu)_TwoAre preferred. Represented by the above general formulas (III) and (IV)
Among the organoaluminum compounds represented by the general formula R⁷ _ThreeIn Al
The compound represented by the formula (1) is preferred, and in particular, R is an isoalkyl group.
Certain compounds are preferred. Olefin polymerization catalyst used in the present invention
Are the components (A), (B-1) (or (B-2)) and
If desired, component (C) can be added in an inert hydrocarbon solvent or
It can be prepared by mixing in a refining solvent.
Wear. Used for preparing catalyst for olefin polymerization
Specific examples of the inert hydrocarbon solvent include propane and pig.
, Pentane, hexane, heptane, octane, deca
, Dodecane, kerosene and other aliphatic hydrocarbons;
Fats such as tan, cyclohexane and methylcyclopentane
Acyclic hydrocarbons; benzene, toluene, xylene, etc.
Aromatic hydrocarbons; ethylene chloride, chlorobenzene, di
Halogenated hydrocarbons such as chloromethane or these
And the like. Each component in preparing the catalyst for olefin polymerization
The mixing order of the minutes is arbitrary, but the component (B-1) (or the component
(B-2)) and component (A) are mixed, or component (B-1) and component
(C) and then component (A).
Minutes (A) and component (B-1) (or component (B-2)),
Then, the component (C) is mixed, or the component (A)
And component (C) are mixed, and then component component (B-1) (also
Is preferably mixed with the component (B-2)). In mixing the above components, the component (B-
Source of aluminum in 1) and transition metal in component (A)
The atomic ratio (Al / transition metal) is usually 10 to 10,000, preferably
Preferably, the concentration is 20 to 5000, and the concentration of the component (A) is
About 10^-8-10^-1Mol / l, preferably 10^-7~
5 × 10^-2It is in the mole / liter range. When the component (B-2) is used, the component (A)
The molar ratio to the component (B-2) (component (A) / component (B-2)) is usually
In the range from 0.01 to 10, preferably from 0.1 to 5,
The concentration of minute (A) is about 10^-8-10^-1Mol / liter,
Preferably 10^-7~ 5 × 10 ^-2In the mole / liter range
is there. When the component (C) is used, the component (C)
Aluminum atom (Al_C) And aluminum in component (B-1)
Atom (Al_B-1) And the atomic ratio (Al_C/ Al_B-1)
Is usually in the range of 0.02 to 20, preferably 0.2 to 10.
It is. Each of the above catalyst components may be mixed in a polymerization vessel.
Alternatively, a mixture obtained in advance may be added to the polymerization vessel.
The mixing temperature when mixing in advance is usually -50 to 150 ° C,
Preferably, it is -20 to 120 ° C, and the contact time is 1 to 1
000 minutes, preferably 5 to 600 minutes. Also,
During the mixing contact, the mixing temperature may be changed. The olefin polymerization catalyst used in the present invention
Is an inorganic or organic, granular or particulate solid
Component (A), Component (B)
And at least one component of component (C) is supported
The solid olefin polymerization catalyst obtained may be used. As the inorganic carrier, a porous oxide is preferred.
For example, SiO_Two, Al_TwoO_ThreeTo illustrate
it can. Granular or particulate solids of organic compounds
Α-oles such as ethylene, propylene and 1-butene
Fin or styrene
A coalescence or a copolymer can be exemplified. The olefin polymerization used in the present invention
The catalyst comprises the above particulate carrier, component (A), component
(B) an olefin polymer formed by prepolymerization and
And optionally an olefin polymer formed from component (C).
It may be a combined catalyst. As the olefin used in the prepolymerization,
Is an olefin such as propylene, ethylene, 1-butene
Is used, but in a mixture of these with other olefins
There may be. The olefin polymerization catalyst according to the present invention
Is useful for olefin polymerization in addition to the above components.
Other components such as water as a catalyst component
be able to. The propylene-based polymer of the present invention comprises
Polymerization of propylene in the presence of a catalyst for olefin polymerization
Can be manufactured. The polymerization is suspension polymerization,
Either liquid phase polymerization such as solution polymerization or gas phase polymerization
Can also be implemented. In the liquid phase polymerization method, the catalyst is used for preparing the above-mentioned catalyst.
Can use the same inert hydrocarbon solvent
In this case, propylene can be used as a solvent. Professional
When performing the suspension polymerization method, the polymerization temperature of pyrene is generally
Usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C.
When performing the solution polymerization method, usually
0-250 ° C, preferably in the range of 20-200 ° C
It is desirable. Also, when performing the gas phase polymerization method,
The polymerization temperature is usually 0 to 120 ° C, preferably 20 to 100 ° C.
It is desirable to be in the range of ° C. The polymerization pressure is usually
Pressure ~ 100kg / cm^Two, Preferably normal pressure to 50 kg /
cm^TwoThe polymerization reaction is batchwise, semi-continuous
It can be carried out in any of the formula and continuous methods
You. Further, the polymerization is performed in two or more stages under different reaction conditions.
It is also possible. The molecular weight of the obtained propylene polymer is
The presence of hydrogen in the polymerization system, or the polymerization temperature and polymerization
It can be adjusted by changing the pressure. [0070] The propylene polymer of the present invention is
High tactical city. Such propylene-based heavy
The coalescence is rigid, heat resistant, surface hardness, gloss, transparency,
Excellent impact strength, various industrial parts, containers, fills
It can be suitably used for rubber, non-woven fabric, drawn yarn and the like. [0071] The present invention will be described in more detail with reference to the following examples.
However, the present invention is not limited to these examples.
Not. [0072] Example 1 Two-liter autoclave sufficiently purged with nitrogen
500 g of propylene is charged to the rave and the temperature is raised to 40 ° C
Then, 0.2 ml of triisobutyl aluminum was added to the reaction system.
Remol, methylaluminoxane 0.2 mmol, rac-di
Phenylsilylbis (2,7-dimethyl-4-isopropyl-1-
Indenyl) zirconium dichloride converted to Zr atom
After adding 0.001 mmol, the temperature was raised to 50 ° C and 1
Polymerization was carried out for hours. After polymerization, degas to remove propylene
The polymer was recovered and dried under reduced pressure at 80 ° C. for 10 hours. The obtained polymer weighed 158 g,
Activity is 158kg polymer / mmol Zr, intrinsic viscosity
[Η] is 4.55 dl / g, and the propane
The triad tacticity of the chain of units is 95.4.
%, Position irregularity based on 2,1-insertion of propylene monomer
The unit ratio is 0.87%, 1,3-insertion of propylene monomer
The percentage of irregular units based on the position is 0.03% or less.
Was.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yoshihisa Kiso 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. JP-A-7-70227 (JP, A) JP-A-7-149832 (JP, A) JP-A-7-138326 (JP, A) JP-A-6-100579 (JP, A) 7-196734 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 C08F 10/00-10/14 C08F 110/00-110/14 C08F 210 / 00-210/18

Claims (1)

(57) [Claims 1] (a) Triad tacticity ( any propylene unit 3 in a polymer chain ) of a propylene unit chain consisting of a head-to-tail bond measured by ¹³ C-NMR. Chained
Among them, the direction of methyl branch in the propylene unit is the same,
And propylene in which each propylene unit is linked head-to-tail
Ratio of emission unit triad sequences) and a 90.0% or more, the proportion of (b) ¹³ was measured by C-NMR, the position-irregular units based on 2,1-insertion of propylene monomer in all propylene insertions 0 0.7 to 2.0% , and the ratio of the position irregular units based on the 1,3-insertion of the propylene monomer is 0.03%.
(C) the intrinsic viscosity measured in decalin at 135 ° C. is 1 to
A propylene-based polymer, which is in a range of 12 dl / g.