JP3423414B2 - Propylene elastomer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a triad tacticity city.
New propylene-based elastomers with high
It is. [0002] BACKGROUND OF THE INVENTION Propylene-based elastomers
Because it is excellent in shock absorption, heat resistance, heat sealability,
In addition to plain use such as films, modifiers for thermoplastic resins
It is used as However, conventional propylene-based elastomers
For simple use, heat sealability, block resistant
Properties and heat resistance are not always sufficient.
If used, the effect of improving impact resistance is not always sufficient
Did not. For this reason, it has excellent impact resistance, etc.
Heat resistance, transparency, heat sealability, blocking resistance, resistance
Propylene elastomer with excellent impact-improving effect
The emergence of is desired. [0004] The present inventors have studied in view of such a situation.
As a result, it contains a specific amount of ethylene units,
Of a propylene chain part consisting of a bond,¹³Measured by C-NMR
High triad tacticity and irregular positioning
Units with a specific ratio and a specific intrinsic viscosity
Pyrene elastomers are found to be excellent in the above properties
As a result, the present invention has been completed. [0005] SUMMARY OF THE INVENTION The present invention provides a triad tacticity
Providing high novel propylene-based elastomers
The purpose is. [0006] SUMMARY OF THE INVENTION A propylene-based elastomer according to the present invention
Is (a) 50 to 95 mol% of propylene units, 5 to 5 of ethylene units
0% by mole, (b)¹³A head-to-tail bond produced by C-NMR
Triad tacticity of the pyrene unit chain represented by the following formula
The city95.0%That's it, Embedded image(c)¹³C-NMR determined total p
Of regio-irregular units based on 2,1-insertion of propylene monomer
Percentage0.5-2.0% And 1,3-insertion of propylene monomer
The proportion of irregular units based on the input is 0.05% or less, (d) The limiting viscosity measured in decalin at 135 ° C is1-12dl / g
In the range. [0007] DETAILED DESCRIPTION OF THE INVENTION
The stoma will be specifically described. The propylene of the present invention
The propylene-based elastomer contains 50 to 95 mol of propylene units.
%, Preferably 60 to 93 mol%, more preferably 70%
９０90 mol%, and ethylene units of 5-50 moles.
%, Preferably 7 to 40 mol%, more preferably 10%
Propylene-ethylene comprising at a rate of .about.30 mol%
It is a random copolymer. [0008] Such a propylene-based elastomer is
Derived from olefins other than propylene and ethylene
For example, in an amount of 10 mol% or less.
Is also good. The propylene-based elastomer of the present invention has a head
A propylene unit chain consisting of a tail bond,¹³C-NM
Triad tacticity measured by R is 90.0% or less
Above, preferably 92.0% or more, more preferably 95.0%.
Desirably, it is 0% or more. Triad tacticity is propylene
Based elastomer¹³From the C-NMR spectrum,
More required. [0011] (Equation 1)[0012]¹³The C-NMR spectrum was measured for samples 50 to 7
0 mg in an NMR sample tube (5 mmφ)
Lobutadiene, o-dichlorobenzene or 1,2,4-tric
About 0.5 ml of rock solution in about 0.5 ml of lorobenzene
Completely dissolved in a solvent containing deuterated benzene as a medium
After that, at 120 ° C, complete proton decoupling
It was measured. Measurement conditions are flip angle 45 °, pal
Interval 3.4T₁(T₁Is the spin lattice of the methyl group
The longest value of the relaxation times). Methylene group and
And methine group T₁Is shorter than the methyl group,
In this case, the recovery of magnetization is 99% or more. Chemical shift
Is the third unit of a 5-chain head-to-tail bonded propylene unit
Was set as 21.59 ppm. Regarding the methyl carbon region (19 to 23 ppm)
The spectrum has a peak region in the first region (21.2 to 2
1.9 ppm), the second region (20.3 to 21.0 pp)
m) and the third region (19.5 to 20.3 ppm).
I can do it. Each peak in the spectrum is described in the literature (Po
lymer,30(1989) 1350). [0014] In the first region, it is indicated by PPP (mm).
The methyl group of the second unit in the three chains of propylene units has resonance
I do. In the second region, the propylene represented by PPP (mr)
A methyl group in the second unit of the three-chain
Units whose units are propylene units and ethylene units
The methyl group (PPE-methyl group) of the pyrene unit has resonance (2
0.7 ppm). [0015] In the third area, it is represented by PPP (rr).
A methyl group in the second unit of the three propylene units, and
Propylene whose adjacent units are all ethylene units
The methyl group (EPE-methyl group) of the unit has resonance (19.8).
ppm). Further, the propylene-based elastomer is
As a partial structure including an irregular unit, the following structure (i)
And (ii). [0017] Embedded image Among them, the carbon A peak and the carbon A 'peak are
The carbon B peak and the carbon B 'peak are in the third region in the second region.
Appears in As described above, peaks appearing in the first to third regions are obtained.
Not based on three head-to-tail bonded propylene units
Peaks are PPE-methyl group, EPE-methyl group, carbon
A, peaks based on carbon A ', carbon B and carbon B'
is there. The peak area based on the PPE-methyl group is:
The peak of the PPE-methine group (resonating around 30.6 ppm)
Peak based on EPE-methyl group
The area is the EPE-methine group (at around 32.9 ppm).
It can be evaluated from the peak area of the ring. Carbon based on carbon A
Is the methine carbon to which the methyl group of carbon B is directly bonded.
(Resonance around 33.6 ppm) from twice the peak area
It can be evaluated, and the peak area based on carbon A 'is
Methine carbon adjacent to methyl group (resonance around 33.2 ppm)
Can be evaluated by the peak area. Peak based on carbon B
The area is the same for adjacent methine carbon (around 33.6 ppm).
The peak area of the
Similarly, the area of the methine carbon (33.2 pp)
(resonance around m). Therefore, these peak areas are defined in the second area.
Head-to-tail
Three linked propylene units (PPP (mr) and
The peak area based on PPP (rr) can be determined.
Wear. As described above, PPP (mm) and PPP (m
Assessing peak areas for r) and PPP (rr)
Can be formed according to the above formula,
Seeking triad tacticity of propylene unit chain
Can be The propylene-based elastomer of the present invention comprises:¹³
2,1-insertion in total propylene insertion measured by C-NMR
The proportion of position irregular units based on is greater than 0.5%,
Preferably 0.5 to 2.0%, more preferably 0.5 to 2.0%
Preferably, it is 1.5%. In addition, the propylene of the present invention
Len based elastomers are based on 1,2-, 1,3-, 1,2-insertions
The position irregularity unit is 0.05% or less, preferably 0.03.
% Is preferable. At the time of polymerization, the propylene monomer has 1,2-insertion
(The methylene side binds to the catalyst), but rarely 2,1-inserted
Sometimes. The 2,1-inserted monomer is
Forms an irregular position unit. Total propylene insertion
2,1-insertion ratio in¹³Using C-NMR, Polyme
r,30(1989) 1350. [0024] (Equation 2) Here, the peaks are named by the method of Carman et al.
(Rubber Chem. Technol.,44(1971), 781). Ma
In addition, Iαβ indicates the peak area such as αβ peak.
You. In addition, due to the overlapping of peaks, Iαβ etc.
Is difficult to determine directly from the spectrum
Can be substituted with a carbon peak with the corresponding area
it can. Based on the 1,2-, 1,3-, 1,2-insertion of propylene
The three-chain amount is the same as the βγ peak (at around 27.4 ppm).
Of the total methyl group peak and the βγ peak
Divide by the sum of 1/2 and multiply by 100 to get the ratio
The combination was determined in%. The propylene elastomer of the present invention comprises:
The intrinsic viscosity [η] measured in decalin at 35 ° C. is 0.1.
To 12 dl / g, preferably 0.5 to 12 dl / g,
More preferably, it is in the range of 1 to 12 dl / g.
New The propylene elastomer of the present invention is
For example, (A) a transition metal compound as described below; (B) (B-1) an organic aluminum oxy compound, and (B-2)
Reaction with the transition metal compound (A) to form an ion pair
At least one compound selected from the group consisting of
As desired (C) Olefin polymerization comprising an organoaluminum compound
Copolymerization of ethylene and propylene in the presence of a catalyst
And can be obtained by Hereinafter, the propylene-based elastomer of the present invention will be described.
Of olefin polymerization catalyst used in the production of olefins
I do. Forming the olefin polymerization catalyst used in the present invention
Transition metal compound (A) (hereinafter referred to as “component (A)”).
Sometimes. ) Is a transition represented by the following general formula (I).
It is a metal compound. [0030] 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;
Organic group; hydroxy group, methoxy, ethoxy, propoxy
Alkoxy group such as butoxy, phenoxy, methyl
Such as phenoxy, dimethylphenoxy, and naphthoxy
Riloxy group, phenylmethoxy, phenylethoxy, etc.
An oxygen-containing group such as an arylalkoxy group;
A sulfur-containing group in which oxygen of a compound is substituted by sulfur; amino
Group, methylamino, dimethylamino, diethylamino,
Dipropylamino, dibutylamino, dicyclohexyl
Alkylamino groups such as amino, phenylamino, diph
Phenylamino, ditolylamino, dinaphthylamino,
Arylamino groups such as tylphenylamino or
Nitrogen-containing groups such as alkylarylamino groups;
Phosphino such as sphino and diphenylphosphino
And a phosphorus-containing group such as a group. 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. As the sulfur-containing group, 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; chloromethyl
The above divalent hydrocarbon group having 1 to 20 carbon atoms such as
Halogenated halogenated hydrocarbon groups; methylsilyl
Dimethylsilylene, diethylsilylene, di (n-pro
Pill) silylene, di (i-propyl) silylene, di (sic)
Rohexyl) silylene, methylphenylsilylene, diph
Phenylsilylene, di (p-tolyl) silylene, di (p-chloro)
Alkylsilylenes such as (rophenyl) silylene, and alkyl
Ruarylsilylene, arylsilylene group, tetramethyl
1,2-disilyl, tetraphenyl-1,2-disilyl, etc.
Of alkyldisilyl, alkylaryldisilyl, ant
A divalent silicon-containing group such as a thiosilyl group;
Divalent Ge in which silicon in the i-containing group is replaced with germanium
Rumanium-containing group; silicon of the above-mentioned divalent silicon-containing group
A divalent tin-containing substituent substituted by tin, and the like;
^FiveIs the R¹, R^TwoHalogen atom and carbon number 1
To 20 hydrocarbon groups, 1 to 20 carbonized halogenated carbons
It is a hydrogen group. 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-bi
1- (2,7-dimethyl-4-ethylindenyl) zircon
Dichloride, rac-dimethylsilyl-bis {1- (2,7
-Dimethyl-4-n-propylindenyl) zirconium di
Chloride, rac-dimethylsilyl-bis {1- (2,7-dimethyl)
Ru-4-i-propylindenyl) zirconium dichloride
, Rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-n-
Butylindenyl) zirconium dichloride, rac-di
Methylsilyl-bis {1- (2,7-dimethyl-4-sec-butylyl)
Ndenyl) zirconium dichloride, rac-dimethyl
Lil-bis {1- (2,7-dimethyl-4-t-butylindenyl)
Le) zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2,7-dimethyl-4-n-pentylindenyl)}
Zirconium dichloride, rac-dimethylsilyl-bis ｛1
-(2,7-dimethyl-4-n-hexylindenyl) zirconi
Um dichloride, rac-dimethylsilyl-bis {1- (2,7-
Dimethyl-4-cyclohexylindenyl) zirconium
Mudichloride, rac-dimethylsilyl-bis {1- (2,7-di
Methyl-4-methylcyclohexylindenyl) zircon
Dichloride, rac-dimethylsilyl-bis {1- (2,7
-Dimethyl-4-phenylethylindenyl) zirconium
Mudichloride, rac-dimethylsilyl-bis {1- (2,7-di
Methyl-4-phenyldichloromethylindenyl) diyl
Conium dichloride, rac-dimethylsilyl-bis ｛1-
(2,7-dimethyl-4-chloromethylindenyl) zircon
Dichloride, rac-dimethylsilyl-bis {1- (2,7
-Dimethyl-4-trimethylsilylmethylindenyl) di
Ruconium dichloride, rac-dimethylsilyl-bis ｛1-
(2,7-dimethyl-4-trimethylsiloxymethylindeni
Le) zirconium dichloride, rac-diethylsilyl-
Bis {1- (2,7-dimethyl-4-i-propylindenyl)}
Zirconium dichloride, rac-di (i-propyl) silyl
Bis {1- (2,7-dimethyl-4-i-propylindenyl)}
Zirconium dichloride, rac-di (n-butyl) silyl bi
1- (2,7-dimethyl-4-i-propylindenyl) di
Ruconium dichloride, rac-di (cyclohexyl) silyl
Rubis ｛1- (2,7-dimethyl-4-i-propylindenyl
Le) zirconium dichloride, rac-methylphenylsi
Rilbis ｛1- (2,7-dimethyl-4-i-propylindenyl
Le) zirconium dichloride, rac-methylphenylsi
Lilbis ｛1- (2,7-dimethyl-4-t-butylindenyl)
Le) zirconium dichloride, rac-diphenylsilyl
Bis {1- (2,7-dimethyl-4-t-butylindenyl)} di
Ruconium dichloride, rac-diphenylsilylbis ｛1-
(2,7-dimethyl-4-i-propylindenyl) zirconi
Um dichloride, rac-diphenylsilylbis {1- (2,7-
Dimethyl-4-ethylindenyl) zirconium dichloro
Lido, rac-di (p-tolyl) silylbis {1- (2,7-dimethyl)
Ru-4-i-propylindenyl) zirconium dichloride
Do, rac-di (p-chlorophenyl) silylbis {1- (2,7-
Dimethyl-4-i-propylindenyl) zirconium di
Chloride, rac-dimethylsilylbis {1- (2-methyl-4-i)
-Propyl-7-ethylindenyl) zirconium dibro
Mido rac-dimethylsilyl-bis {1- (2-methyl-4-i-pro
Pyr-7-methylindenyl) zirconium dimethyl, r
ac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-
7-methylindenyl) zirconium methyl chloride,
rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl)
-7-methylindenyl) zirconium-bis (methanes
Ruphonato), rac-dimethylsilyl-bis {1- (2-methyl-
4-i-propyl-7-methylindenyl) zirconium-bi
(P-phenylsulfinato), rac-dimethylsilyl-
Bis ｛1- (2-ethyl-4-i-propyl-7-methylindeni
Le) zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-phenyl-4-i-propyl-7-methylindeni)
Le) zirconium dichloride. 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 compound as described above
Of zirconium metal to titanium metal and hafnium
Metal, vanadium metal, niobium metal, tantalum metal,
Place on chromium metal, molybdenum metal, tungsten metal
Altered transition metal compounds 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
To the organic aluminum compound and the adsorbed water or
A method of reacting water of crystallization. (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. [0047] (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. The solvent used for the aluminoxane solution
Benzene, toluene, xylene, cumene,
Aromatic hydrocarbons, pentane, hexane, hepta
Octane, decane, dodecane, hexadecane, octane
Aliphatic hydrocarbons such as tadecane, cyclopentane,
Rohexane, cyclooctane, methylcyclopentane
Petroleum such as alicyclic hydrocarbons, gasoline, kerosene, light oil
Distillate or the above aromatic hydrocarbons, aliphatic hydrocarbons, fats
Aliphatic hydrocarbon halides, especially chlorinated compounds, bromine
And hydrocarbon solvents such as chlorides. Other, ethyl
Using ethers such as ether and tetrahydrofuran
You can also. Among these solvents, especially aromatic hydrocarbons
Preferred are aliphatic and aliphatic hydrocarbons. 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. ))
Gazette, Japanese Patent Application Laid-Open No. 1-5020206,
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,
Borane compounds can be mentioned. 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. The organic aluminum 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, -S
iR¹⁴ _ThreeGroup or -N (R^Fifteen) AlR¹⁶ _TwoAnd n is
1-2, R^Ten, R¹¹, R¹²And R¹⁶Is methyl
Group, ethyl group, isopropyl group, isobutyl group, cyclo
A hexyl group or a phenyl group;¹³Is a hydrogen atom,
Methyl group, ethyl group, isopropyl group, phenyl group,
A methylsilyl group or the like;¹⁴And R^FifteenIs meth
And an ethyl group. ) Such an organic aluminum
Among the compounds, R⁷ _nAl (OALR)^Ten _Two)_3-n
A compound represented by, for example, Et_TwoAlOAlEt_Two, (I
so-Bu)_TwoAlOAl (iso-Bu)_TwoAre preferred. The compounds represented by the above general formulas (III) and (IV)
Among the organoaluminum compounds represented by the general formula R⁷ _ThreeWith Al
The compound represented by the formula (1) is preferred, and in particular, R is an isoalkyl group.
Certain compounds are preferred. The 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 preparation of 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)). When 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
0.01 to 10, preferably in the range of 0.1 to 5,
The concentration of component (A) is about 10^-8-10^-1Mol / lit
, Preferably 10^-7~ 5 × 10^-2Mole / liter range
It is an enclosure. 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 an enclosure. 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 catalyst for olefin polymerization used in the present invention
Is an inorganic or organic compound having a granular or
Represents the above components in a particulate carrier that is a particulate solid.
(A), at least one of component (B) and component (C)
A catalyst for solid olefin polymerization in which a component is supported
There may be. 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 elastomer of the present invention
Propylene and ethylene in the presence of the olefin polymerization catalyst described above.
Can be produced by copolymerizing with
You. Copolymerization is a liquid phase polymerization method such as suspension polymerization and solution polymerization
Alternatively, it can be carried out by any of the gas phase polymerization methods. In the liquid phase polymerization method, the catalyst is used for preparing the above-mentioned catalyst.
Can use the same inert hydrocarbon solvent
Propylene and / or ethylene as solvent
You can also be. The copolymerization temperature of propylene and ethylene is
When performing the suspension polymerization method, usually -50 ~ 100 ℃,
The temperature is preferably in the range of 0 to 90 ° C.
When performing the liquid polymerization method, it is usually 0 to 250 ° C., preferably
Preferably, it is in the range of 20 to 200 ° C. Ma
When the gas phase polymerization method is carried out, the copolymerization temperature is usually 0.
To 120 ° C, preferably 20 to 100 ° C.
Is desirable. Copolymerization pressure is usually from normal pressure to 100 kg
/ Cm^Two, Preferably normal pressure to 50 kg / cm^TwoUnder the conditions
Yes, copolymerization reaction can be batch, semi-continuous, or continuous
It can also be performed in these methods. Further copolymerization
It is also possible to carry out the reaction in two or more stages with different reaction conditions.
You. The molecules of the propylene-based elastomer obtained
The amount depends on whether hydrogen is present in the copolymer
It can be adjusted by changing the temperature and copolymerization pressure.
Can be. [0074] The propylene elastomer of the present invention is
High readability. Such propylene
Series elastomers are heat-resistant, shock-absorbing, transparent,
Excellent sealability and blocking resistance.
Modification of thermoplastic resin in addition to plain use for systems and sheets
It can be suitably used for materials and the like. [0075] 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. The heat sealing start temperature and the heat
Sheet seal starting temperature, film impact strength and
Izod strength was measured as follows.Heat sealing start temperature Using the obtained polymer, 30 m with a T-die attached
mφ uniaxial extruder, width 30cm, thickness 50μm
Film. The molding conditions were as follows: resin temperature: 210 ° C. (extruder
Die part), take-off speed: 3 m / powder, cooling roll: 2
5 ° C. Two sheets of the obtained film are superimposed and a width of 5
2kg / cm using a 2mm seal bar^Two1 second at pressure
Heat-sealed at various different temperatures
Was. A test piece having a width of 15 mm was cut out from this sample, and 23
Peeling rate of the heat-sealed part at a temperature of 200 ° C.
Peeling force when peeling under conditions of 180 ° C
Heats the temperature of the seal bar to 300 g / 25 mm
The seal start temperature (° C.) was set. [0078]Heat seal starting temperature after heat treatment Two films heat-sealed under the same conditions as above
After heat treatment at 50 ° C. for 7 days, peel off in the same manner as above.
Measure the peeling resistance and the peeling resistance becomes 300g / 25mm
Heat sealer temperature after heat treatment
The starting temperature was used. [0079]Film impact strength Molded in the same manner as the measurement of the heat sealing start temperature
Using a film, a film impact tester (Toyo
(Manufactured by Seiki). In addition, the impact head portion of the tester
Is 1/2 inch φ (12.7 mm φ). [0080]Izod impact strength 20 parts by weight of the obtained polymer and Mitsui Petrochemical Industry Co., Ltd.
Company-made polypropylene HIPOL^TMGrade J700
[Melt flow rate (230 ° C) 11g / 10min, density
0.91 g / cm^Three) Dry blend with 80 parts by weight
And kneaded at 200 ° C using a twin-screw extruder.
The ren composition was adjusted. The resulting polypropylene composition
Using an injection molding machine, resin temperature 200 ° C, mold temperature 4
An ASTM molded piece was molded at 0 ° C
The impact strength (IZ) was measured according to ASTM 256
Was. Measurement temperature: 23 ° C. Test piece: 12.7 mm (width) x 6.4 mm (thickness) x
64mm (length) The notch was machined. [0082]Melt flow rate (MFR) Polypropylene prepared when measuring Izod impact strength
The composition is loaded according to ASTM D1238.
The weight was measured at 2.16 kg and the temperature at 230 ° C. [0083] Example 1 Two-liter autoclave sufficiently purged with nitrogen
900ml of hexane is charged to the tribe.
Propylene in a gas
The feed was 60 liters. After heating to 70 ° C,
Feed the ren and make the total pressure 8kg / cm^TwoBoost to -G,
Methylaluminoxane 0.45 mmol, rac-diphenyl
Lucylyl bis 1- (2,7-dimethyl-4-isopropylin
Denyl)｝ Convert zirconium dichloride to Zr atom
0.0015 mmol, and ethylene was continuously added to the filter.
8kg / cm total pressure^Two-40 minutes while keeping G
Was performed. After polymerization, deaerate and po
The limmer was recovered and dried under reduced pressure at 110 ° C. for 10 hours. The obtained polymer weighed 47.2 g,
Synthetic activity: 31.5 kg polymer / mmol Zr, ultimate viscosity
Degree [η] = 2.0 dl / g, ethylene content = 27.0 m
%, Propylene unit chain consisting of head-tail bonds
Adacticity = 95.4%, propylene monomer
The proportion of irregularly positioned units based on the 2,1-insertion of
%, Position irregularity based on 1,3-insertion of propylene monomer
The unit ratio was 0.05% or less. Also obtained
The physical properties of the polymer were measured. [0085] [Example 2] 2 liters of autoclave sufficiently purged with nitrogen
900ml of hexane is charged to the tribe.
Was added and the temperature was raised to 70 ° C.
Then, feed ethylene to 2.0 kg / cm^TwoPressurized
And feed propylene to increase the total pressure to 8 kg / cm.^Two-G
And 0.3 mmol of methylaluminoxane, rac-dim
Tylsilyl bis {1- (2,7-dimethyl-4-isopropyl)
Ndenyl)｝ Convert zirconium dichloride to Zr atom
0.001 mmol, and propylene was continuously added.
Feed and total pressure kg / cm^Two10 minutes while maintaining -G
Was performed. After polymerization, deaerate and po
The limmer was recovered and dried under reduced pressure at 110 ° C. for 10 hours. The obtained polymer weighed 16.8 g,
Synthetic activity: 16.8 kg polymer / mmol Zr, ultimate viscosity
Degree [η] = 1.7 dl / g, ethylene content = 8.5 mol
%, A triad of a propylene chain part comprising a head-to-tail bond
Cutity = 95.6%, 2,2 of propylene monomer
The percentage of irregularly-positioned units based on 1-insertion is 0.62%,
The regioregular unit based on the 1,3-insertion of propylene monomer is
Was 0.05% or less. Also, the obtained polymer
The physical properties of the polymer were measured. Table 1 shows the above results. [0087] [Table 1]

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Junichi Imuta 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industries Co., Ltd. (72) Yoshihisa Kiso, Inventor Kuga-gun, Yamaguchi Prefecture 6-1-2 Kimachi Waki Mitsui Petrochemical Industries, Ltd. (72) Inventor Mikio Hashimoto 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industries Co., Ltd. (56) Reference Document JP-A-5-306304 (JP, A) JP-A-7-149834 (JP, A) JP-A-62-119215 (JP, A) Polymer, 1989, Vol. 30, No. 7, pp. 1350-1356 (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 C08F 10/00-10/14 CA (STN) REGISTRY (STN)

Claims (1)

(57) Claims: (1) A head comprising 50 to 95 mol% of a propylene unit and 5 to 50 mol% of an ethylene unit, and (b) a head obtained by ¹³ C-NMR. A triad tacticity represented by the following formula of a propylene unit chain portion comprising a tail bond is 95.0 % or more; (c) Determined by ¹³ C-NMR, the proportion of regio- irregular units based on the 2,1-insertion of the propylene monomer in the total propylene insertion is 0.5 to 2.0% , and the 1,3-insertion of the propylene monomer (D) at 135 ° C., the intrinsic viscosity measured in decalin is 1 to 12 d1 / g.
A propylene-based elastomer characterized by the following range: