JP3570772B2 - Sealant - Google Patents

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel propylene-based elastomer having excellent rigidity, heat resistance, scratch resistance, transparency, heat sealability, and blocking property.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
Propylene-based elastomers are used for films, sheets, and the like because of their excellent scratch resistance, transparency, heat resistance, heat sealability, and the like.
[0003]
Among such propylene-based elastomers, a propylene-based elastomer which is a copolymer of propylene and 1-butene is a conventional solid titanium-based catalyst or a metallocene-based metallocene compound comprising a metallocene compound such as zirconium or hafnium and an alkylaluminoxane. Manufactured using a catalyst.
[0004]
However, the conventional propylene-based elastomer produced as described above was not always sufficient in heat sealability, blocking resistance, and heat resistance. For this reason, there has been a demand for a propylene-based elastomer having excellent shock absorption, heat resistance, transparency, and rigidity, as well as excellent heat sealability and blocking resistance.
[0005]
The present inventors have studied propylene-based elastomers, which are copolymers of propylene and 1-butene, in view of such conventional techniques. It has been found that a propylene-based elastomer having high tail-bonding and all methyl groups having the same branching direction) and high stereoregularity exhibits the above-mentioned excellent properties. The inventors have found that such a propylene-based elastomer can be efficiently produced by using a specific metallocene compound catalyst component, and have completed the present invention.
[0006]
The present applicant has previously disclosed in Japanese Patent Application Laid-Open No. 62-119212 a propylene-based elastomer in which propylene and other α-olefins are regularly head-to-tail bonded. This propylene-based elastomer is manufactured using a metallocene compound such as ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, and has a composition (compared to the propylene-based elastomer according to the present invention). If the comonomer ratios are the same, they have a higher melting point.
[0007]
[Object of the invention]
An object of the present invention is to provide a novel propylene-based elastomer having excellent rigidity, heat resistance, scratch resistance, transparency, heat sealability, and blocking property.
[0008]
Summary of the Invention
The sealant according to the present invention,
(1) a unit derived from propylene in an amount of 70 to 90 mol%, a unit derived from 1-butene in an amount of 10 to 30 mol%,
(2) (i) three head-to-tail linked propylene units, or
(ii) in a propylene-butene three chain consisting of a head-tail bonded propylene unit and a butene unit, and having a propylene unit as the second unit;
About the side chain methyl group of the propylene unit of the second unit¹³A C-NMR spectrum (based on hexachlorobutadiene solution and tetramethylsilane) was measured, and a peak appearing at 21.0 to 21.9 ppm when the total area of the peak appearing at 19.5 to 21.9 ppm was taken as 100%. Area is 90% or more,
(3) the intrinsic viscosity measured in decalin at 135 ° C. is 0.1 to 12 dl / g;
(4) the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 3 or less;
(5) The parameter B value indicating the randomness of the copolymer monomer chain distribution is 1.0 to 1.3,
(6) The melting point Tm measured by a differential scanning calorimeter is 60~ 105.1 ° CAnd the relationship between the melting point Tm and the 1-butene structural unit content M (mol%) is
−2.6M + 125 ≦ Tm ≦ −2.6M + 145,
(7) The relationship between the crystallinity C measured by the X-ray diffraction method and the 1-butene structural unit content M (mol%) is as follows:
C ≧ −1.5M + 65
Characterized by comprising a propylene-based elastomer.
[0010]
In the sealant according to the present invention as described above, the propylene-based elastomer includes:
[A]The following general formula [I] or [ II A metallocene compound represented by the formula:,
[B] [B-1] an organoaluminum oxy compound, and / or
[B-2] a compound which reacts with the metallocene compound [A] to form an ion pair;
Optionally, in the presence of a catalyst for olefin polymerization containing [C] an organoaluminum compound,
Desirably, it is obtained by copolymerizing propylene and 1-butene.
[0014]
Embedded image
[0015]
[Wherein, M is a transition metal of Groups IVB, VB and VIB of the periodic table,
R¹¹And R¹²May be the same or different from each other, and R in the formula (A)¹Is the same as
R^ThirteenAnd R¹⁴May be the same or different from each other, and are an alkyl group or an aryl group having 1 to 20 carbon atoms,
X¹, X², Y are the same as in the above formula (A). ]
[0016]
Embedded image
[0017]
Wherein M is a transition metal of Group IVB of the periodic table;
R²¹May be the same or different from each other, and may be a hydrogen atom, a halogen atom, an optionally halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or -NR.₂, -SR, -OSiR₃, -SiR₃Or -PR₂A group (where R is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms);
R²²~ R²⁸Is the above R²¹The same as or adjacent R²²~ R²⁸May form an aromatic- or aliphatic ring together with the atoms to which they are attached, and X³And X⁴May be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. An alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an OH group or a halogen atom,
[0018]
Embedded image
[0019]
-Sn-, -O-, -S-, = SO, = SO₂, = NR²⁹, = CO, = PR²⁹Or = P (O) R²⁹It is. (However, R²⁹And R³⁰May be the same as or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 6 to 10 carbon atoms. A fluoroaryl group, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms or an alkyl having 7 to 40 carbon atoms An aryl group or R²⁹And R³⁰May form a ring together with the atoms to which they are attached,²Is silicon, germanium or tin. )].
[0020]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the propylene-based elastomer according to the present invention will be specifically described.
(1) The propylene-based elastomer according to the present invention is a random copolymer of propylene and 1-butene,
50 to 95 mol%, preferably 60 to 93 mol%, more preferably 70 to 90 mol% of units derived from propylene,
It contains units derived from 1-butene in an amount of 5 to 50 mol%, preferably 7 to 40 mol%, more preferably 10 to 30 mol%.
[0021]
This propylene-based elastomer may contain a small amount of units derived from olefins other than propylene and 1-butene, for example, 10 mol% or less, preferably 5 mol% or less.
[0022]
(2) Stereoregularity of propylene elastomer (triad tacticity: mm fraction)
The stereoregularity of the propylene-based elastomer according to the present invention can be evaluated by triad tacticity (fraction in mm).
[0023]
This mm fraction is defined as a ratio in which the direction of methyl group branching is the same when three head-to-tail bonded propylene unit chains present in a polymer chain are represented by a surface zigzag structure. To^ThirteenIt is determined from a C-NMR spectrum.
[0024]
This mm fraction is^ThirteenWhen determined from the C-NMR spectrum, specifically as a three-chain containing propylene units present in the polymer chain,
(I) three chains of head-to-tail linked propylene units, and
(Ii) 3 chains of a propylene unit / butene unit consisting of a head-tail bonded propylene unit and a butene unit and the second unit being a propylene unit
For, the mm fraction is measured.
[0025]
The mm fraction is determined from the peak intensity of the side chain methyl group of the second unit (propylene unit) in these three chains (i) and (ii). This will be described in detail below.
Propylene elastomer^ThirteenThe C-NMR spectrum is measured by completely dissolving propylene-based elastomer in hexachlorobutadiene containing a small amount of deuterated benzene as a lock solvent in a sample tube at 120 ° C. by a proton complete decoupling method. The measurement conditions were a flip angle of 45 ° and a pulse interval of 3.4T.₁(T₁Is the longest value of the methyl group spin lattice relaxation times). T of methylene and methine groups₁Is shorter than the methyl group, so that under this condition, the recovery of magnetization of all carbons in the sample is 99% or more. The chemical shift was determined by setting the methyl group carbon peak of the third unit of five chains (mmmm) of propylene units head-to-tail bonded to tetramethylsilane as 21.593 ppm, and the other carbon peaks as a reference.
[0026]
The propylene elastomer measured in this way^ThirteenIn the C-NMR spectrum, a methyl carbon region (about 19.5 to 21.9 ppm) in which a side chain methyl group of a propylene unit is observed,
A first peak region (about 21.0 to 21.9 ppm),
A second peak area (about 20.2 to 21.0 ppm),
It is classified into the third peak region (about 19.5 to 20.2 ppm).
[0027]
In each of these regions, the side chain methyl group peak of the second unit (propylene unit) in the three molecular chains (i) and (ii) having head-to-tail bonds as shown in Table 1 is observed.
[0028]
[Table 1]
[0029]
In the table, P represents a unit derived from propylene, and B represents a unit derived from 1-butene.
Of the three head-to-tail linkages (i) and (ii) shown in Table 1, (i) PPP (mm), PPP (mr), and PPP (rr) in which all three The directions are shown below in the form of a surface zigzag structure. (Ii) The mm, mr, and rr bonds of three chains (PPB, BPB) containing butene units conform to this PPP.
[0030]
Embedded image
[0031]
In the first region, the methyl group of the second unit (propylene unit) in the mm-coupled PPP, PPB, and BPB chains resonates.
In the second region, the methyl group of the second unit (propylene unit) in the mr-bonded PPP, PPB, and BPB three chains and the methyl group of the second unit (propylene unit) in the rr-bonded PPB and BPB three chains resonate. I do.
In the third region, the methyl group of the second unit (propylene unit) of the rr-bonded three-chain PPP resonates.
[0032]
Therefore, the triad tacticity (mm fraction) of the propylene-based elastomer is
(I) three head-to-tail linked propylene units, or
(Ii) a propylene-butene three-chain consisting of a head-to-tail bonded propylene unit and a butene unit, and including a propylene unit in the second unit;
Regarding the side chain methyl group of the propylene unit of the second unit in the three chains,^ThirteenWhen measured by C-NMR spectrum (based on hexachlorobutadiene solution and tetramethylsilane),
When the total area of peaks appearing at 19.5 to 21.9 ppm (methyl carbon region) is defined as 100%,
The ratio (percentage) of the area of the peak appearing at 21.0 to 21.9 ppm (first region) is obtained from the following equation.
[0033]
(Equation 1)
[0034]
The propylene-based elastomer according to the present invention has a mm fraction thus obtained of 90% or more, preferably 92% or more, more preferably 94% or more.
The propylene-based elastomer has a position irregular unit represented by the following structures (iii), (iv) and (v), in addition to the above-mentioned three chains (i) and (ii) having head-to-tail bonds. And a peak derived from the side chain methyl group of the propylene unit due to such another bond is also observed in the above methyl carbon region (19.5 to 21.9 ppm). .
[0035]
Embedded image
[0036]
Of the methyl groups derived from the above structures (iii), (iv) and (v), the methyl group carbon A and the methyl group carbon B resonate at 17.3 ppm and 17.0 ppm, respectively. The peak based on B does not appear in the first to third regions (19.5 to 21.9 ppm). Furthermore, since both carbon A and carbon B do not participate in the propylene tri-chain based on the head-to-tail bond, they need not be considered in the above calculation of triad tacticity (mm fraction).
[0037]
Further, a peak based on methyl group carbon C, a peak based on methyl group carbon D and a peak based on methyl group carbon D ′ appear in the second region, and a peak based on methyl group carbon E and a peak based on methyl group carbon E ′ are Appears in the third area.
[0038]
Accordingly, the first to third methyl carbon regions include a PPE-methyl group (a side chain methyl group in a propylene-propylene-ethylene chain) (around 20.7 ppm) and an EPE-methyl group (a side chain in an ethylene-propylene-ethylene chain). Peaks based on (chain methyl group) (around 19.8 ppm), methyl group C, methyl group D, methyl group D ', methyl group E and methyl group E'.
[0039]
As described above, in the methyl carbon region, peaks of methyl groups not based on the head-to-tail bond triple chains (i) and (ii) are also observed. Is corrected as follows.
[0040]
The peak area based on the PPE-methyl group can be determined from the peak area of the PPE-methine group (resonating at around 30.6 ppm), and the peak area based on the EPE-methyl group is determined by the EPE-methine group (around 32.9 ppm). At the resonance).
[0041]
The peak area based on the methyl group C can be determined from the peak area of an adjacent methine group (resonating around 31.3 ppm).
The peak area based on the methyl group D can be determined from 和 of the sum of the peak areas based on the αβ methylene carbon of the structure (iv) (resonance at around 34.3 ppm and around 34.5 ppm). The peak area based on the methyl group D 'can be determined from the area of the peak (resonating around 33.3 ppm) based on the methine group adjacent to the methyl group of the methyl group E' in the structure (v).
[0042]
The peak area based on the methyl group E can be determined from the peak area of the adjacent methine carbon (resonating around 33.7 ppm), and the peak area based on the methyl group E ′ can be calculated from the adjacent methine carbon (around 33.3 ppm). (Resonance) peak area.
[0043]
Therefore, by subtracting these peak areas from the total peak areas of the second region and the third region, the peak area of the methyl group based on the three head-to-tail bonded propylene unit chains (i) and (ii) can be obtained. .
[0044]
As described above, the peak area of the methyl group based on the three head-to-tail bonded propylene unit chains (i) and (ii) can be evaluated, so that the mm fraction can be obtained according to the above equation.
Note that each carbon peak in the spectrum is described in the literature (Polymer,30, 1350 (1989)).
[0045]
(3) Intrinsic viscosity [η]
The propylene-based elastomer according to the present invention has an intrinsic viscosity [η] measured at 135 ° C. in decalin of 0.1 to 12 dl / g, preferably 0.5 to 12 dl / g, more preferably 1 to 12 dl / g. .
[0046]
(4) Molecular weight distribution
The propylene-based elastomer according to the present invention has a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography GPC of 3 or less, preferably 2.0 to 3.0, more preferably 2.0 to 2.5. It is.
[0047]
(5) Randomness
The propylene-based elastomer according to the present invention has a parameter B value indicating the randomness of the copolymer monomer chain distribution of 1.0 to 1.5, preferably 1.0 to 1.3, more preferably 1.0 to 1.2. It is.
[0048]
This parameter B value is determined by Coleman et al. (BD Cole-man and TG Fox, J. Polym. Sci.,Al, 3183 (1963)), and is defined as follows.
B = P₁₂/ (2P₁・ P₂)
Where P₁, P₂Are the first and second monomer content fractions, respectively,₁₂Is the ratio of the (first monomer)-(second monomer) chain in the entire bimolecular chain.
When the B value is 1, Bernoulli statistics are followed. When B <1, the copolymer is block-like, and when B> 1, the copolymer is alternate.
[0049]
The propylene-based elastomer according to the present invention, in addition to the above properties,
(6) It is desirable that the melting point Tm measured by a differential scanning calorimeter is 60 to 140 ° C, preferably 80 to 130 ° C, and
The relationship between the melting point Tm and the 1-butene structural unit content M (mol%) is as follows.
-2.6M + 125 ≦ Tm ≦ −2.6M + 145.
[0050]
(7) The relationship between the crystallinity C measured by the X-ray diffraction method and the 1-butene constituent unit content M (mol%) is as follows.
It is desirable that C ≧ −1.5M + 65.
[0051]
The propylene-based elastomer according to the present invention as described above,
(8) The propylene chain may have a small amount of a structure containing a heterogeneous bonding unit (positionally irregular unit) based on 2,1-insertion or 1,3-insertion of propylene present in the propylene chain.
[0052]
At the time of polymerization, propylene is usually 1,2-inserted (the methylene side is bonded to the catalyst) to form a head-to-tail bonded propylene chain as described above. May be inserted. The 2,1-inserted and 1,3-inserted propylene form regio-irregular units in the polymer as shown by structures (iii), (iv) and (v) above. The ratio of 2,1-insertion and 1,3-insertion of propylene in the polymer constitutional unit may be the same as in the above-mentioned stereoregularity.^ThirteenUsing the C-NMR spectrum, Polymer,30, 1350 (1989).
[0053]
The ratio of the position irregular units based on 2,1-insertion of propylene can be obtained from the following equation.
[0054]
(Equation 2)
[0055]
When it is difficult to determine the area of Iαβ or the like directly from the spectrum due to the overlap of peaks, the correction can be made with a carbon peak having the corresponding area.
[0056]
In the propylene-based elastomer according to the present invention, the heterogeneous bonding unit based on the 2,1-insertion of propylene present in the propylene chain determined as described above is specifically 0.01% or more of all the propylene structural units. It may be contained at a rate of about 0.01 to 1.0%.
[0057]
The proportion of the position irregular units based on the 1,3-insertion of propylene in the propylene-based elastomer can be determined from the βγ peak (resonance around 27.4 ppm).
[0058]
In the propylene-based elastomer according to the present invention, the proportion of heterogeneous bonds based on 1,3-insertion of propylene may be 0.50% or less.
The propylene-based elastomer according to the present invention as described above,
[A] a specific metallocene compound,
[B] [B-1] an organic aluminum oxy compound, and / or
[B-2] a compound reacting with the metallocene compound [A] to form an ion pair;
If desired, it can be obtained by copolymerizing propylene and 1-butene in the presence of an olefin polymerization catalyst comprising [C] an organoaluminum compound.
[0059]
Hereinafter, the olefin polymerization catalyst used in the present invention will be described.
[A] Metallocene compound
The propylene-based elastomer according to the present invention is produced using a metallocene compound [A] represented by the following general formula (A).
[0060]
Embedded image
[0061]
In the formula, M is a transition metal belonging to Groups IV to VIB of the periodic table, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten, and preferably titanium, zirconium, Hafnium, particularly preferably zirconium.
[0062]
Substituent R ¹ ~ R ⁴
R¹, R², R³And R⁴May be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, and a nitrogen-containing group. Alternatively, it may be a phosphorus-containing group, and a part of groups adjacent to each other may be bonded to form a ring together with the carbon atom to which those groups are bonded. Note that R is displayed two each.¹~ R⁴Indicates that when these are combined to form a ring, it is preferable to combine them by a combination of the same symbols.¹And R¹And to form a ring.
[0063]
Specifically, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
As the hydrocarbon group having 1 to 20 carbon atoms, for example,
Alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, and adamantyl Group,
Alkenyl groups such as vinyl, propenyl and cyclohexenyl,
Benzyl, phenylethyl, arylalkyl groups such as phenylpropyl,
Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, And aryl groups such as biphenylyl.
[0064]
The ring formed by combining these hydrocarbon groups includes a condensed group such as a benzene ring, a naphthalene ring, an acenaphthene ring, and an indene ring; and a hydrogen atom on a condensed group such as a benzene ring, a naphthalene ring, an acenaphthene ring, and an indene ring. Examples thereof include groups in which atoms are substituted with an alkyl group such as methyl, ethyl, propyl, and butyl.
[0065]
Further, these hydrocarbon groups may be substituted with halogen.
As the silicon-containing group, monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, and dimethylphenyl Trihydrocarbon-substituted silyls such as silyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl;
Silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether,
Examples include a silicon-substituted alkyl group such as trimethylsilylmethyl, and a silicon-substituted aryl group such as trimethylphenyl.
[0066]
Examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy, an allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy, and an arylalkoxy group such as phenylmethoxy and phenylethoxy.
[0067]
Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing compound has been replaced with sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, and trimethylbenzene sulfonate. Sulfonate groups such as phonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, and p-toluenesulfinate , Trimethylbenzenesulfinate, pentafluorobenzenesulfinate and the like.
[0068]
Examples of the nitrogen-containing group include an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and dicyclohexylamino; and an aryl group such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino. Examples include an amino group or an alkylarylamino group.
[0069]
Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino.
X ¹ And X ²
X¹And X²Is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by halogen, an oxygen-containing group or a sulfur-containing group. As these atoms or groups, specifically, R¹~ R⁴And the same atoms or groups as those shown in.
[0070]
Y
Y is a divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen, a divalent silicon-containing group, a divalent germanium-containing group, -O-, -CO-, -S-, -SO-, -SO₂-, -NR⁷-, -P (R⁷)-, -P (O) (R⁷)-, -BR⁷-Or -AlR⁷-. (However, R⁷Is a hydrogen atom, a halogen atom as described above, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by halogen. )
Specifically, examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, and 1,4-tetramethylene. Examples include an alkylene group such as methylene, 1,2-cyclohexylene, and 1,4-cyclohexylene, and an arylalkylene group such as diphenylmethylene and diphenyl-1,2-ethylene. Further, a halogenated hydrocarbon group obtained by halogenating the above-mentioned divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene is exemplified.
[0071]
Examples of the divalent silicon-containing group include methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, and di (p Alkylsilylenes such as -tolyl) silylene and di (p-chlorophenyl) silylene, alkylarylsilylenes, arylsilylene groups, alkyldisilyls such as tetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl, and alkylaryls And disilyl and aryldisilyl groups.
[0072]
Examples of the divalent germanium-containing group include compounds in which silicon of the above-mentioned divalent silicon-containing group is substituted with germanium.
In the present invention, among the metallocene compounds represented by the above formula (A), a metallocene compound represented by the following formula [I] is preferably used.
[0073]
Embedded image
[0074]
Substituent R ¹¹ And R ¹²
R¹¹And R¹²May be the same or different from each other, and in the formula (A), R¹~ R⁴Is the same as
[0075]
Substituent R ^Thirteen And R ¹⁴
R^ThirteenAnd R¹⁴May be the same or different and are an alkyl group or an aryl group having 1 to 20 carbon atoms. The alkyl group or the aryl group includes R¹¹And R¹²And the same groups as those described above.
[0076]
These alkyl groups or aryl groups may be substituted with a halogen or an organic silyl group (silicon-containing group).
Among these, a secondary or tertiary alkyl group and an aryl group having 6 to 15 carbon atoms are preferable.
[0077]
X ¹ And X ²
X¹And X²Is the same as in the above formula (A).
Among these, a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms are preferable.
[0078]
Y
Y is the same as in the above formula (A).
Of these, a divalent silicon-containing group, a divalent germanium-containing group is preferable, a divalent silicon-containing group is more preferable, and alkylsilylene, alkylarylsilylene, and arylsilylene are more preferable.
[0079]
Hereinafter, specific examples of the metallocene compound represented by the above general formula [I] will be shown.
rac-dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4,6-diphenyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-phenyl-6-isopropyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-α-naphthyl-6-isopropyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-methyl-6-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-methyl-6-i-propyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4,6-di (i-propyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4,6-di (sec-butyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-ethyl-4,6-di (i-propyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-n-propyl-4,6-di (i-propyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4,6-di (i-propyl) -1-indenyl) titanium dichloride,
rac-dimethylsilylene-bis (2-methyl-4,6-di (i-propyl) -1-indenyl) hafnium dichloride and the like.
[0080]
The indene derivative ligand of the metallocene compound represented by the formula [I] as described above can be synthesized, for example, by a usual organic synthesis technique by the following reaction steps.
[0081]
Embedded image
[0082]
The metallocene compound used in the present invention can be obtained from the indene derivative obtained as described above, for example, from Journal of Organometallic Chem. 288 (1985), pp. 63-67, and JP-A-4-268307.
[0083]
Further, in the present invention, as the metallocene compound [A], a compound represented by the following formula [II] described in EP-549900 and Canada-2084017 can also be used.
[0084]
Embedded image
[0085]
In the formula, M is a transition metal atom of Group IVB of the periodic table, specifically, titanium, zirconium, or hafnium, and particularly preferably zirconium.
R²¹May be the same or different from each other, and may be a hydrogen atom, a halogen atom, preferably a fluorine atom or a chlorine atom, an optionally halogenated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, Preferably 6 to 8 aryl groups, -NR₂, -SR, -OSiR₃, -SiR₃Or -PR₂(Where R is a halogen atom, preferably a chlorine atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms).
[0086]
R²²~ R²⁸May be the same or different, and R²¹Are the same atoms or groups as²²~ R²⁸And at least two groups adjacent to each other may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded.
[0087]
X³And X⁴May be the same or different from each other,
Hydrogen atom, halogen atom, OH group,
An alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms,
An alkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms,
An aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms;
An aryloxy group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms;
An alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms;
An arylalkyl group having 7 to 40, preferably 7 to 10 carbon atoms,
An alkylaryl group having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms;
An arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms.
[0088]
Embedded image
[0089]
-Sn-, -O-, -S-, = SO, = SO₂, = NR²⁹, = CO, = PR²⁹Or = P (O) R²⁹It is.
Where R²⁹And R³⁰May be the same or different from each other,
Hydrogen atom, halogen atom,
An alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly a methyl group,
A fluoroalkyl group having 1 to 10 carbon atoms, preferably CF₃Group,
An aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms;
An aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms;
A fluoroaryl group having 6 to 10 carbon atoms, preferably a pentafluorophenyl group,
An alkoxy group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly a methoxy group,
An alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms;
An arylalkyl group having 7 to 40, preferably 7 to 10 carbon atoms,
An arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms;
An arylalkyl group having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms.
[0090]
Also R²⁹And R³⁰And may form a ring together with the atoms to which they are bonded.
M²Is silicon, germanium or tin.
[0091]
The above-mentioned alkyl group is a linear or branched alkyl group, and the halogen (halogenated) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, particularly a fluorine atom or a chlorine atom.
[0092]
Among the compounds represented by the formula [II],
M is zirconium or hafnium;
R²¹Are the same as each other, are alkyl groups having 1 to 4 carbon atoms,
R²²~ R²⁸May be the same or different from each other, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
X³And X⁴May be the same or different from each other, and are an alkyl group having 1 to 3 carbon atoms or a halogen atom,
[0093]
Embedded image
[0094]
(M²Is silicon and R²⁹And R³⁰May be the same or different and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. )
Is preferred,
Substituent R²²And R²⁸Is a hydrogen atom, and R²³~ R²⁷Is more preferably a compound having an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.
[0095]
Further, M is zirconium,
R²¹Are the same alkyl groups having 1 to 4 carbon atoms,
R²²And R²⁸Is a hydrogen atom,
R²³~ R²⁷May be the same or different and are an alkyl group having 1 to 4 carbon atoms or a hydrogen atom,
X³And X⁴Are chlorine atoms,
[0096]
Embedded image
[0097]
(M²Is silicon and R²⁹And R³⁰May be the same or different and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. )
Are preferred, and in particular,
M is zirconium,
R²¹Is a methyl group,
R²²~ R²⁸Is a hydrogen atom,
X³And X⁴Is a chlorine atom,
[0098]
Embedded image
[0099]
Are preferred.
Hereinafter, specific examples of the metallocene compound represented by the formula [II] will be shown.
rac-dimethylsilylene-bis (4,5-benzo-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-α-acenaphth-1-indenyl) zirconium dichloride;
rac-dimethylsilylene-bis (2,3,6-trimethyl-4,5-benzo-1-indenyl) zirconium dichloride,
rac-methylphenylsilylene-bis (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride,
rac-diphenylsilylene-bis (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride,
rac-diphenylsilylene-bis (2-methyl-α-acenaphth-1-indenyl) zirconium dichloride;
rac-methylphenylsilylene-bis (2-methyl-α-acenaphth-1-indenyl) zirconium dichloride,
rac-1,2-ethanediyl-bis (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride,
rac-1,2-ethanediyl-bis (2-methyl-α-acenaphth-1-indenyl) zirconium dichloride,
rac-1,2-butanediyl-bis (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride,
rac-1,2-butanediyl-bis (2-methyl-α-acenaphth-1-indenyl) zirconium dichloride and the like.
[0100]
In addition, compounds in which zirconium in the above compounds is replaced with titanium or hafnium can also be mentioned.
In the present invention, a racemic metallocene compound represented by the formula [I] or [II] is generally used as a catalyst component, but an R-type or S-type may also be used.
[0101]
The above metallocene compounds may be used in combination of two or more.
In the present invention, among these, as the metallocene compound [A],
rac-dimethylsilylene-bis (2-methyl-4,6-diisopropyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-α-acenaphth-1-indenyl) zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride is particularly preferably used.
[0102]
[B-1] Organic aluminum oxy compounds
[B-1] The organoaluminum oxy compound (hereinafter sometimes referred to as “component [B-1]”) forming the olefin polymerization catalyst used in the present invention may be a conventionally known aluminoxane. Alternatively, a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-2-78687 may be used.
[0103]
A conventionally known aluminoxane can be produced, for example, by the following method.
(1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of the above to react.
(2) A method in which water, ice, and steam are allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, and tetrahydrofuran.
(3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.
[0104]
The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in a solvent or suspended in a poor solvent for aluminoxane.
[0105]
Specific examples of the organoaluminum compound used in preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum, tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, trialkyl aluminum such as tridecyl aluminum, tricyclohexyl aluminum, tricycloalkyl aluminum such as tricyclooctyl aluminum,
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride,
Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide,
Examples include dialkylaluminum aryloxides such as diethylaluminum phenoxide.
[0106]
Of these, trialkyl aluminum and tricycloalkyl aluminum are preferred, and trimethyl aluminum is particularly preferred.
Further, as an organoaluminum compound used for preparing an aluminoxane, isoprenyl aluminum represented by the following general formula can also be used.
[0107]
(I-C₄H₉)_xAl_y(C₅H₁₀)_z      ... [II]
(Where x, y, and z are positive numbers and z ≧ 2x).
The above-mentioned organoaluminum compounds can be used in combination of two or more kinds.
[0108]
Solvents used for the solution or suspension of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Hydrogen, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil; and halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Hydrocarbon solvents such as chlorides, bromides and the like. In addition, ethers such as ethyl ether and tetrahydrofuran can be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.
[0109]
[B-2] Compounds that form ion pairs
[B-2] Forming Catalyst for Olefin Polymerization Used in the Present Invention [B-2] A compound that reacts with the metallocene compound [A] to form an ion pair (hereinafter may be referred to as “component [B-2]”. ) Are described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, and JP-A-3-207704. And Lewis acids, ionic compounds and carborane compounds described in JP-A-547718.
[0110]
Examples of the Lewis acid include triphenyl boron, tris (4-fluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, and tris (pentafluorophenyl). ) Boron, MgCl₂, Al₂O₃, SiO₂-Al₂O₃And the like.
[0111]
Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and ferrocenium tetraborate. (Pentafluorophenyl) borate and the like can be exemplified.
[0112]
Examples of the carborane compound include dodecaborane, 1-carboundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarboundeca) borate, and tri-n-butylammonium (trideca) Hydride-7-carboundeca) borate and the like.
[0113]
The compound [B-2] that forms an ion pair by reacting with the metallocene compound as described above can be used in combination of two or more.
[C] Organoaluminum compound
In the present invention, when forming the catalyst for olefin polymerization, [C] an organoaluminum compound (hereinafter sometimes referred to as “component [C]”) may be used, if desired. ], For example, an organoaluminum compound represented by the following general formula [III] can be mentioned.
[0114]
R⁹ _nAlX_3-n  ... [III]
(Where R⁹Is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3. )
Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group and an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group Hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.
[0115]
Specific examples of such an organoaluminum compound [C] include the following compounds.
Trialkyl aluminums such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri (2-ethylhexyl) aluminum, and tridecyl aluminum;
Alkenyl aluminum such as isoprenyl aluminum,
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, etc.
Alkyl aluminum sesquichlorides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide,
Alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide,
Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride;
[0116]
Further, as the organoaluminum compound [C], a compound represented by the following general formula [IV] can also be used.
R⁹ _nAll_3-n  … [IV]
(Where R⁹Is the same as above, and L is -OR¹⁰Group, -OSiR¹¹ ₃Group, -OAlR¹² ₂Group, -NR^Thirteen ₂Group, -SiR¹⁴ ₃Group or -N (R^Fifteen) AlR¹⁶ ₂N is 1-2, R¹⁰, R¹¹, R¹²And R¹⁶Is a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc.^ThirteenRepresents a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilylene group or the like;¹⁴And R^FifteenRepresents a methyl group, an ethyl group or the like. )
Among such organoaluminum compounds,
R⁷ _nAl (OALR)¹⁰ ₂)_3-nA compound represented by, for example,
Et₂AlOAlEt₂, (Iso-Bu)₂AlOAl (iso-Bu)₂Are preferred.
[0117]
Among the organoaluminum compounds represented by the general formulas [III] and [IV], the general formula R⁷ ₃Compounds represented by Al are preferred, and especially R⁷Is preferably an isoalkyl group.
[0118]
The catalyst for olefin polymerization used in the present invention comprises the component [A], the component [B-1] (or the component [B-2]) and, if desired, the component [C] in an inert hydrocarbon solvent or an olefin solvent. It can be prepared by mixing.
[0119]
As the inert hydrocarbon solvent used for preparing the catalyst for olefin polymerization, specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, methyl Examples thereof include alicyclic hydrocarbons such as cyclopentane, aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures thereof.
[0120]
The mixing order of each component when preparing the olefin polymerization catalyst is arbitrary,
Mixing the component [B-1] or the component [B-2]) with the component [A],
Mixing the component [B-1] with the component [C] and then mixing the component [A], or
Mixing the component [A] with the component [B-1] (or the component [B-2]) and then mixing the component [C], or
It is preferable to mix the component [A] and the component [C] and then mix the component [B-1] (or the component [B-2]).
[0121]
When mixing the above components, the atomic ratio (Al / transition metal) of aluminum in the component [B-1] to the transition metal in the component [A] is usually 10 to 10000, preferably 20 to 5000. And the concentration of component (A) is about 10^-8-10^-1Mol / l, preferably 10^-7~ 5 × 10^-2It is in the mole / liter range.
[0122]
When the component [B-2] is used, the molar ratio of the component [A] to the component [B-2] (component [A] / component [B-2]) is usually 0.01 to 10, preferably 0 to 10. And the concentration of component [A] is about 10-10.^-8-10^-1Mol / l, preferably 10^-7~ 5 × 10^-2It is in the mole / liter range.
[0123]
When the component [C] is used, the aluminum atom (Al_C) And the aluminum atom (Al) in component [B-1]_B-1) And the atomic ratio (Al_C/ Al_B-1) Is generally in the range of 0.02 to 20, preferably 0.2 to 10.
[0124]
The above-mentioned respective catalyst components may be mixed in a polymerization vessel, or a mixture obtained in advance may be added to the polymerization vessel.
The mixing temperature at the time of pre-mixing is usually -50 to 150C, preferably -20 to 120C, and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes. Further, the mixing temperature may be changed during the mixing contact.
[0125]
The catalyst for olefin polymerization used in the present invention is prepared by adding at least one of the above-mentioned components [A], [B] and [C] to an inorganic or organic, particulate carrier which is a granular or particulate solid. It may be a solid olefin polymerization catalyst in which the components are supported.
[0126]
As the inorganic carrier, a porous oxide is preferable.₂, Al₂O₃
And the like.
Examples of the granular or particulate solid of the organic compound include α-olefins such as ethylene, propylene, and 1-butene, and polymers or copolymers formed mainly from styrene.
[0127]
The olefin polymerization catalyst used in the present invention includes the above-mentioned particulate carrier, component [A], component [B], an olefin polymer produced by preliminary polymerization, and an olefin polymerization catalyst formed from component [C] if desired. It may be.
[0128]
As the olefin used for the prepolymerization, olefins such as propylene, ethylene, and 1-butene are used, but a mixture of these with other olefins may be used.
[0129]
The olefin polymerization catalyst used in the present invention may contain, in addition to the above components, other components useful for olefin polymerization, such as water as a catalyst component.
[0130]
The propylene-based elastomer according to the present invention can be produced by copolymerizing propylene and 1-butene in the presence of the above-mentioned olefin polymerization catalyst so that the final composition ratio is attained.
[0131]
The polymerization can be carried out by any of a liquid phase polymerization method such as suspension polymerization and solution polymerization or a gas phase polymerization method.
In the liquid phase polymerization method, the same inert hydrocarbon solvent as used in the above catalyst preparation can be used, and propylene can be used as the solvent.
[0132]
The polymerization temperature is usually in the range of −50 to 100 ° C., preferably 0 to 90 ° C. when performing the suspension polymerization method, and usually 0 to 250 ° C. when performing the solution polymerization method. C, preferably in the range of 20 to 200C. When carrying out the gas phase polymerization method, the polymerization temperature is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C.
[0133]
The polymerization pressure is usually from normal pressure to 100 kg / cm.², Preferably normal pressure to 50 kg / cm²The polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system.
[0134]
Further, the polymerization can be performed in two or more stages having different reaction conditions.
The molecular weight of the obtained propylene-based elastomer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature and the polymerization pressure.
[0135]
【The invention's effect】
The propylene-based elastomer according to the present invention has high triad tacticity, excellent rigidity, heat resistance, scratch resistance, transparency, heat sealability, and blocking resistance, and is preferably used for sheets, films, and the like. And can be suitably used especially as a sealant.
[0136]
In particular, the film containing the propylene-based elastomer according to the present invention does not change its heat-sealing temperature over time even when it is stored for a long period of time, so that a stable heat-sealing operation is ensured.
[0137]
Further, the propylene-based elastomer according to the present invention has a lower melting point than the conventional elastomer when the composition ratio of propylene and 1-butene is the same. Can be Further, the propylene-based elastomer molded article according to the present invention has a high surface hardness, and thus is hardly scratched.
[0138]
【Example】
Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
[0139]
[Physical property measurement method]
[1-butene content]
^ThirteenIt was determined using C-NMR.
[0140]
[Intrinsic viscosity [η]]
Measured in decalin at 135 ° C. and expressed in dl / g.
[Molecular weight distribution (Mw / Mn)]
The molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C manufactured by Millipore.
[0141]
The separation column was TSK GNH HT, the column size was 27 mm in diameter and 600 mm in length, the column temperature was 140 ° C., and the mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries) and BHT (BHT) as an antioxidant. (Takeda Pharmaceutical Co., Ltd.) Using 0.025% by weight, the sample was moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene has a molecular weight of Mw <1000 and Mw> 4 × 10⁶About 1000 <Mw <4 × 10⁶Was used by Pressure Chemical Company.
[0142]
[B value]
Note that the composition distribution B value is the value of a sample in which about 200 mg of a copolymer is uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube.^ThirteenThe C-NMR spectrum is usually measured under the measurement conditions of a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, a spectrum width of 1500 Hz, a filter width of 1500 Hz, a pulse repetition time of 4.2 sec, and an integration frequency of 2000 to 5000 times, From this spectrum, P_E, P_o, P_OEWas calculated.
[0143]
[Triad Tacticity City]
Hexachlorobutadiene solution (based on tetramethylsilane)^ThirteenThe C-NMR spectrum was measured, and the ratio (%) of the area of the peak appearing at 21.0 to 21.9 ppm to the total area (100%) of the peak appearing at 19.5 to 21.9 ppm was determined.
[0144]
[Rate of heterogeneous bond based on 2,1-insertion]
Polymer,30, 1350 (1989)) by the method described above.^ThirteenIt was determined using a C-NMR spectrum.
[0145]
[Melting point (Tm)]
Approximately 5 mg of a sample is packed in an aluminum pan, heated to 200 ° C. at 10 ° C./min, kept at 200 ° C. for 5 minutes, cooled to room temperature at 20 ° C./min, and then heated at 10 ° C./min. It was determined from the curve. The measurement was performed using a DSC-7 type device manufactured by PerkinElmer.
[0146]
[Crystallinity]
It was determined by X-ray diffraction measurement of a 1.0 mm thick pressed sheet that had passed at least 24 hours after molding.
[0147]
[Heat sealing start temperature]
▲ 1 ▼ Creation of film
An aluminum sheet having a thickness of 0.1 mm, a PET sheet, and an aluminum sheet having a thickness of 100 μm obtained by cutting the center into 15 cm × 15 cm squares are laid in this order on a press plate, and are laid in the center (the cut-out portion). A 3.3 g sample was placed. Next, a PET sheet, an aluminum plate, and a press plate are further stacked in this order.
[0148]
The sample sandwiched between the press plates is placed in a 200 ° C. hot press, preheated for about 7 minutes, and then pressurized (50 kg / cm) to remove air bubbles in the sample.²G) Repeat the depressurization operation several times. Then finally 100kg / cm²Pressurize to G and heat under pressure for 2 minutes. After depressurization, the press plate was taken out of the press machine, transferred to another press machine having a crimped portion kept at 0 ° C., and moved to 100 kg / cm.²After pressurized and cooled at G for 4 minutes, the pressure is released and the sample is taken out. The obtained film having a uniform thickness of about 150 to 170 μm is used for measuring the heat seal strength.
[0149]
(2) Measurement of heat seal strength
The film is cut into strips having a width of 15 mm, the two sheets are overlapped, and this is further sandwiched between two Teflon films having a thickness of 0.1 mm, followed by heat sealing. Heat sealing is performed by maintaining the temperature of the lower portion of the heat seal at a constant 70 ° C. and changing only the temperature of the upper portion of the hot plate in steps of 5 ° C. as appropriate. Pressure during heat sealing is 2kg / cm²The heat sealing time is 1 second and the sealing width is 5 mm (therefore, the sealing area is 15 mm × 5 mm).
[0150]
The heat seal strength is obtained by performing a tensile test at a tensile speed of 30 cm / min on the peel strength of the film heat-sealed at each of the above heat seal temperatures.
[0151]
The peel strength at each heat sealing temperature in increments of 5 ° C. is determined by the method described above, and a plot of the heat sealing temperature versus the peel strength is connected by a curve. Based on this curve, the heat seal temperature at which the peel strength is 300 g / 15 cm is defined as the heat seal start temperature.
[0152]
(3) Measurement of heat seal strength of aging treatment
The aging treatment of the film is performed by placing the film in a constant temperature bath at 50 ° C. for 7 days. When aging, attach paper to both sides of the film so that the films do not touch each other. The heat-sealing start temperature of the film subjected to the aging treatment is measured by the method described above.
[0153]
[Martens hardness]
The Martens hardness is measured by using a Martens scratch tester manufactured by Tokyo Koki Co., Ltd., with a trace of a 1 mm press sheet surface being scratched by applying a constant load (5 g) to the diamond weight. The test specimens were measured for the width of the scratches using a microscope, and the reciprocal (mm^-1) Is determined, and it is defined as Martens hardness.
[0154]
[Blocking stress]
Evaluation was performed according to ASTM D1893. Two 10 cm wide and 15 cm long films are cut out and stacked. This is sandwiched between two glass plates, loaded with a load of 10 kg, and left in an air oven at 50 ° C. After 7 days, the sample was taken out, the peel strength was measured, and the peel strength per cm was defined as a blocking value.
[0155]
[Haze]
The film prepared for measuring the heat sealing start temperature was measured according to ASTM D1003-61.
[0156]
[Production Example 1]
[Production of dimethylsilylene-bis (2-methyl-α-acenaphth-1-indenyl) zirconium dichloride (metallocene compound represented by formula [II])]
In an Ar atmosphere, AlCl₃120 g (0.900 mol), CS₂600 ml of the mixture was cooled to 5 ° C. in an ice bath and stirred.
[0157]
To this, 110 g (0.714 mol) of acenaphthene was added, and after stirring for 5 minutes, 90 ml (0.921 mol) of methacryloyl chloride and CS were added using a dropping funnel.₂100 ml of the mixture were added over 1 hour. After completion of the dropwise addition, the mixture was further stirred at 5 ° C. for 1 hour. The reaction solution was poured into ice water, and the product was extracted with ether. The ether phase is saturated NaHCO₃After washing with water followed by saturated aqueous NaCl,₂SO₄And then concentrated. The resulting viscous oil is CH₂Cl₂Purified by silica gel column using hexane as a developing solvent to obtain 61 g (0.275 mol, 31% yield) of ketone (a) represented by the following formula as a semi-solid.
[0158]
Embedded image
[0159]
The physical properties of the obtained product are shown below.
M⁺      222
IR (KBr) 1690cm^-1
NMR (CDCl₃1.36 (3H, d, J = 7 Hz), 3.43 (4H, s), 7.24 (1H, s) 7.38 (1H, d, J = 8 Hz) 7.62 (1H, t) , J = 8 Hz) 8.58 (1H, d, J = 8 Hz)
Under an Ar atmosphere, 25 g (0.113 mol) of the ketone (a) and 500 ml of anhydrous tetrahydrofuran were put into a three-necked flask and cooled to 5 ° C. in an ice bath. LiAlH₄  3.2 g (0.084 mol) were added in small portions over 20 minutes. After the addition was completed, the mixture was stirred at 5 ° C for 2 hours. After adding celite to the reaction mixture, carefully add saturated NH₄Cl water is added and excess LiAlH₄Was disassembled.
[0160]
Na₂SO₄After stirring for 10 minutes, the reaction mixture was filtered using a funnel covered with Celite. Residue CH₂Cl₂And the filtrate was concentrated to obtain 26 g of a pale yellow solid. This solid is CH₂Cl₂After passing through a short silica gel column, the mixture was concentrated to obtain 24 g (0.107 mmol, yield 95%) of a stereoisomer mixture of alcohol (b) represented by the following formula.
[0161]
Embedded image
[0162]
The alcohol (b) was subjected to a dehydration reaction without further purification to obtain an olefin (c). That is, a mixture of 8.80 g (39.29 mmol) of alcohol (b), 100 ml of benzene, and 100 mg (0.53 mmol) of p-toluenesulfonic acid was heated and stirred at 40 ° C. for 20 minutes in an Ar atmosphere. K is added to the reaction mixture.₂CO₃And Na₂SO₄Was added, and the mixture was filtered using a funnel covered with Celite.
[0163]
Residue CH₂Cl₂And the filtrate was concentrated to obtain 7.92 g of crude olefin 3. This crude product is treated with hexane, CH₂Cl₂Was purified with a silica gel column as a developing solvent to obtain 7.10 g (34.5 mmol, yield 88%) of an olefin (c) represented by the following formula as a semisolid.
[0164]
Embedded image
[0165]
The physical properties of the obtained product are shown below.
M⁺      206
NMR (CDCl₃) 2.24 (3H, bs), 3.41 (6H, bs), 6.98 (1H, bs), 7.22 (1H, d, J = 8 Hz), 7.36 (1H, s), Under an atmosphere of 7.42 (1 H, t, J = 8 Hz) and 7.70 (1 H, d, J = 8 Hz), 6.01 g (29.17 mmol) of olefin (c), 84 ml of anhydrous ether, 72 mg of CuCN ( (0.80 mmol) was cooled in an ice bath, and into this, 20.54 ml (32.04 mmol) of a 1.56 M n-BuLi hexane solution was added using a dropping funnel over 30 minutes. After the addition, the ice bath was removed, and the mixture was stirred at room temperature for 1.5 hours. To this, a solution of 1.97 ml (16.03 mmol) of dimethyldichlorosilane in 5 ml of anhydrous ether was added over 25 minutes, and then stirred at room temperature for 16 hours. After cooling the reaction mixture in an ice bath, water was added, the ether phase was separated, and the aqueous phase was₂Cl₂Extracted. Ether and CH₂Cl₂Combined phases and Na₂SO₄, And concentrated to obtain a crude silylated product. This crude silylated product is converted to CH₂Cl₂Rinsing purification was performed with -hexane (1: 8 v / v) to obtain 5.19 g (11.09 mmol, yield 79%) of a silylated product (d) represented by the following formula as a white solid.
[0166]
Embedded image
[0167]
The physical properties of the obtained product are shown below.
M⁺      468
mp 191-194 ° C
NMR (CDCl₃2.) -0.39, -0.35, -0.27 (total 6H, s each), 2.33, 2.39 (total 6H, s each) 3.39 (8H, bs); 97 (2H, bs) 7.03 to 7.93 (10H, m)
Under an Ar atmosphere, a mixture of 2.00 g (4.27 mmol) of the silylated product (d) and 120 ml of anhydrous tetrahydrofuran was cooled to −50 ° C. using a dry ice-acetone bath, and a 1.56 M n-BuLi hexane solution 5 was added. .47 ml (8.53 mmol) was added over 20 minutes using a dropping funnel. After completion of the dropwise addition, the bath was removed, and the mixture was stirred at room temperature for 1.5 hours. After distilling off tetrahydrofuran under reduced pressure, 40 ml of anhydrous hexane was added, and after stirring, the pressure was reduced again and hexane was distilled off. After cooling the reaction vessel to -50 ° C using a dry ice-acetone bath, CH at -30 ° C was used.₂Cl₂Is added, followed by ZrCl₄Was added, and stirring was continued for 16 hours. The reaction mixture is filtered and the residue is CH₂Cl₂, And the filtrate was concentrated to obtain 2.30 g of a crude product.
[0168]
This crude product is treated with tetrahydrofuran and CH₂Cl₂When purified using₂Cl₂400 mg (0.64 mmol, 15% yield) of racemic dimethylsilylene-bis (2-methyl-α-acenaphth-1-indenyl) zirconium dichloride represented by the following formula was obtained as a soluble, insoluble matter in tetrahydrofuran.
[0169]
Embedded image
[0170]
The physical properties of the obtained product are shown below.
M⁺    626
NMR (CDCl₃1.) 1.36 (6H, s), 2.37 (6H, s), 3.20-3.50 (8H, m) 7.10-7.75 (10H, m)
[0171]
[Reference Example 1]
A 2-liter autoclave sufficiently purged with nitrogen was charged with 900 ml of hexane and 70 g of 1-butene, and 1 mmol of triisobutylaluminum was added. After heating to 70 ° C., propylene was supplied to give a total pressure of 14 kg / cm 2.^TwoG, 0.40 mmol of methylaluminoxane and 0.002 mmol of rac-dimethylsilylene-bis (2-methyl-α-acenaphth-1-indenyl) zirconium dichloride obtained in Production Example 1 in terms of Zr atom were added. , Continuous supply of propylene to a total pressure of 14 kg / cm^TwoThe polymerization was carried out for 60 minutes while maintaining at G.
[0172]
After the polymerization, the polymer was degassed, and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours.
The obtained polymer (propylene-based elastomer) was 89.2 g, and the polymerization activity was 45 kg · polymer / mmol Zr · hr. This polymer contained 8.2 mol% of units derived from 1-butene. The intrinsic viscosity [η] was 1.82 dl / g, and the melting point was 115.8 ° C. The percentage of heterogeneous bonds based on the 2,1-insertion was about 0.38%.
[0173]
Table 2 shows the physical properties measured for the obtained polymer.
[0174]
【Example1]
A 2-liter autoclave sufficiently purged with nitrogen was charged with 900 ml of hexane and 100 g of 1-butene, 1 mmol of triisobutylaluminum was added, and the temperature was raised to 70 ° C.^TwoG, 0.30 mmol of methylaluminoxane and 0.002 mmol of rac-dimethylsilylene-bis (2-methyl-α-acenaphth-1-indenyl) zirconium dichloride obtained in Production Example 1 in terms of Zr atom were added. , Continuous supply of propylene to a total pressure of 14 kg / cm^TwoThe polymerization was carried out for 60 minutes while maintaining at G.
[0175]
After the polymerization, the polymer was degassed, and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours.
The obtained polymer (propylene-based elastomer) was 65.3 g, and the polymerization activity was 33 kg · polymer / mmol Zr · hr. This polymer contained 13.0 mol% of units derived from 1-butene. The intrinsic viscosity [η] was 1.81 dl / g, and the melting point was 102.3 ° C. The percentage of heterogeneous bonds based on the 2,1-insertion was about 0.36%. Table 2 shows the physical properties measured for the obtained polymer.
[0176]
【Example2]
A 2-liter autoclave sufficiently purged with nitrogen was charged with 950 ml of hexane and 130 g of 1-butene, and 1 mmol of triisobutylaluminum was added. After heating to 70 ° C., propylene was supplied to supply a total pressure of 14 kg / cm.^TwoG, 0.30 mmol of methylaluminoxane and 0.002 mmol of rac-dimethylsilylene-bis (2-methyl-α-acenaphth-1-indenyl) zirconium dichloride obtained in Production Example 1 in terms of Zr atom were added. , Continuous supply of propylene to a total pressure of 14 kg / cm^TwoThe polymerization was carried out for 60 minutes while maintaining at G.
[0177]
After the polymerization, the polymer was degassed, and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours.
The obtained polymer (propylene-based elastomer) was 44.0 g, and the polymerization activity was 22 kg · polymer / mmol Zr · hr. This polymer contained 17.7 mol% of units derived from 1-butene. The intrinsic viscosity [η] was 1.79 dl / g, and the melting point was 89.1 ° C. The percentage of heterogeneous bonds based on the 2,1-insertion was about 0.35%.
[0178]
Table 2 shows the physical properties measured for the obtained polymer.
[0179]
[Comparative Example 1]
A 2-liter autoclave sufficiently purged with nitrogen was charged with 830 ml of hexane and 100 g of 1-butene, and 1 mmol of triisobutylaluminum was added thereto.²G, 1 mmol of triethylaluminum and 0.005 mmol of a titanium catalyst supported on magnesium chloride in terms of Ti atoms, and propylene is continuously supplied to give a total pressure of 7 kg / cm.²While maintaining at G, polymerization was carried out for 30 minutes. After the polymerization, the polymer was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours.
[0180]
The obtained polymer was 33.7 g, and the polymerization activity was 14 kg · polymer / mmol Zr · hr. This polymer contained 25.3 mol% of units derived from 1-butene. The intrinsic viscosity [η] was 1.89 dl / g, and the melting point was 110.0 ° C. The percentage of heterogeneous bonds based on the 2,1-insertion was below the detection limit.
[0181]
Table 2 shows the physical properties measured for the obtained polymer.
[0182]
[Table 2]
[0183]
[Production Example 2]
[Synthesis of rac-dimethylsilylene-bis (2-methyl-4,6-diisopropyl-1-indenyl) zirconium dichloride (metallocene compound represented by formula [I])]
( 2- Methyl -4,6- Synthesis of diisopropyl) indene (compound (1))
123 g (0.92 mol) of aluminum chloride and 200 ml of carbon disulfide were charged into a 1-liter reactor sufficiently purged with nitrogen, and 78 ml (0.41 mol) of 1,3-diisopropylbenzene and 45 ml of methacryloyl chloride (45 ml) were added thereto. (0.41 mol) with 40 ml of carbon disulfide was added dropwise at 20-25 ° C. After reacting at room temperature for 12 hours, the reaction mixture was added to 1 kg of ice and extracted with ether. After washing the obtained ether solution with saturated aqueous sodium hydrogen carbonate, the ether layer was further washed with water and the ether layer was concentrated to obtain 68 g of an oil. When this oil was purified by silica gel column chromatography (developing solvent: n-hexane), 43 g of a mixture of 2-methyl-4,6-diisopropyl-1-indanone and 2-methyl-5,7-diisopropyl-1-indanone was obtained. Was obtained (yield: 47%).
[0184]
3.3 g (86 mmol) of sodium borohydride and 40 ml of ethyl alcohol are charged into a 1-liter reactor sufficiently purged with nitrogen. It was added dropwise at 50 ° C. After the completion of the dropwise addition, the mixture was reacted at 60 ° C. for 1 hour and at 70 ° C. for 2 hours. Then, 30 ml of acetone was added while cooling the reaction solution with water. After the reaction solution was concentrated and dried, 300 ml of ether and 100 ml of water were added to perform extraction. The ether layer was washed with water and dried over anhydrous sodium sulfate. The ether layer was concentrated and then dried to obtain 21.1 g of a pale yellow viscous alcohol (yield: 99%).
[0185]
The above-mentioned alcohol (21.0 g, 79 mmol) and benzene (500 ml) were charged into a 1-liter reactor which had been sufficiently purged with nitrogen, and paratoluenesulfonic acid monohydrate (50 mg, 0.55 mmol) was added thereto, followed by 1 hour Refluxed. After completion of the reaction, the mixture was poured into 300 ml of a saturated aqueous sodium hydrogen carbonate solution, and the ether layer was washed with water and dried over anhydrous sodium sulfate. The ether layer was concentrated and dried under reduced pressure to obtain 19 g of the target indene derivative as a pale yellow-green oil. The oil was purified by silica gel column chromatography (developing solvent: n-hexane) to obtain 17.6 g of the desired indene derivative (1) as a colorless amorphous (yield: 95%).
[0186]
NMR (CDCl₃, Ppm):
δ = 1.32 (3H, d, J = 7.2 Hz), 2.16 (3H, s), 2.74-3.20 (2H, m), 3.28 (2H, m), 6. 60 (1H, s), 6.98 (1H, s), 7.12 (1H, s)
1,1'- Dimethylsilylene − Screw( 2- Methyl -4,6- Synthesis of diisopropylindene) (compound (2))
A 200 ml reactor sufficiently purged with nitrogen was charged with 7.0 g (31 mmol) of compound (1), 76 mg (0.9 mmol) of copper cyanide, and 60 ml of diethyl ether, and cooled to -10 ° C. A hexane solution of n-butyllithium (31 mmol) was added to this solution. After the temperature was raised to room temperature, the mixture was cooled again to −10 ° C., 1.9 ml (15.5 mmol) of dimethyldichlorosilane was added dropwise over 30 minutes, and the reaction was carried out for 1 hour. After completion of the reaction, the mixture was added to 40 ml of a saturated aqueous solution of ammonium chloride, extracted with n-hexane, washed with water and dried over magnesium sulfate. The yellow oil obtained by removing the salt and concentrating the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: n-hexane) to obtain 6.1 g of compound (2) as a colorless amorphous. (Yield: 73%).
[0187]
NMR (CDCl₃, Ppm):
δ = 1.25 to 1.40 (30H, m), 2.18 (3H, s), 2.24 (3H, s), 2.92 (2H, q, J = 6.8 Hz), 3. 23 (2H, q, J = 6.8 Hz), 3.65 (2H, br.s), 6.73 (2H, br.s), 6.97 (2H, br.s), 7.10 7.23 (2H, br.s)
rac- Dimethylsilylene − Screw( 2- Methyl -4,6- Synthesis of diisopropylindenyl) zirconium dichloride
Into a 300 ml reactor sufficiently purged with nitrogen, 5.9 g (12.2 mmol) of the compound (2) obtained above and 100 ml of tetrahydrofuran were charged, cooled to -78 ° C and stirred. To this, 15.4 ml of n-butyllithium (n-hexane solution, 1.58N, 24.4 mmol) was added dropwise over 20 minutes, and the mixture was stirred for 1 hour while maintaining the temperature to prepare an anion solution. Thereafter, the temperature was slowly raised to room temperature.
[0188]
At the same time, 100 ml of tetrahydrofuran was charged into a 300 ml reactor sufficiently purged with nitrogen, cooled to -78 ° C, and stirred. After 2.85 g (12.2 mmol) of zirconium tetrachloride was slowly added thereto, the temperature was raised to room temperature. The above-mentioned anion solution was added dropwise thereto over 30 minutes, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the mixture was concentrated under reduced pressure, and the precipitated solid was washed three times with 300 ml of hexane to remove insolubles. The obtained hexane solution was concentrated to about 50 ml and cooled at 6 ° C. for 12 hours. Remove the precipitated solid and remove the resulting solution¹As a result of analysis by 1 H-NMR, it was a mixture (9: 1) of a racemic form and a meso form. 150 ml of hexane was added to the mixture, and recrystallization was performed again to obtain 0.15 g of the above target compound as yellow columnar crystals (yield: 2%).
[0189]
The result of FD mass spectrometry of the obtained compound was 644 (M⁺)Met.
NMR (CDCl₃, Ppm):
δ = 1.28 (6H, s) 1.20 to 1.36 (24H, m), 2.85 (2H, q, J = 6.8 Hz), 3.04 (2H, q, J = 6. 8Hz), 6.80 (2H, s), 7.05 (2H, s), 7.26 (2H, s)
[0190]
[Reference Example 2]
A 2-liter autoclave sufficiently purged with nitrogen was charged with 900 ml of hexane and 70 g of 1-butene, and 1 mmol of triisobutylaluminum was added. After heating to 70 ° C., propylene was supplied to give a total pressure of 14 kg / cm 2.^TwoG, 0.40 mmol of methylaluminoxane, rac-dimethylsilylene-bis (2-methyl-4,6-diisopropyl-1-indenyl) zirconium dichloride prepared in Production Example 2 was converted to Zr atom at 0.002. Mmol, and continuously supply propylene to increase the total pressure to 14 kg / cm.^TwoThe polymerization was carried out for 60 minutes while maintaining at G.
[0191]
After the polymerization, the polymer was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours.
The obtained polymer (propylene-based elastomer) was 31.7 g, and the polymerization activity was 16 kg · polymer / mmol Zr · hr. The polymer contained 6.2 mol% of units derived from 1-butene. The intrinsic viscosity [η] was 1.83 dl / g, and the melting point was 118.2 ° C. The percentage of heterogeneous bonds based on the 2,1-insertion was about 0.88%.
[0192]
Table 3 shows the physical properties measured for the obtained polymer.
[0193]
【Example3]
A 2-liter autoclave sufficiently purged with nitrogen was charged with 900 ml of hexane and 100 g of 1-butene, 1 mmol of triisobutylaluminum was added, and the temperature was raised to 70 ° C.^TwoG, 0.30 mmol of methylaluminoxane, rac-dimethylsilylene-bis (2-methyl-4,6-diisopropyl-1-indenyl) zirconium dichloride produced in Production Example 2 was converted to Zr atom at 0.002. Mmol, and continuously supply propylene to increase the total pressure to 14 kg / cm.^TwoThe polymerization was carried out for 60 minutes while maintaining at G.
[0194]
After the polymerization, the polymer was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours.
The obtained polymer (propylene-based elastomer) was 19.0 g, and the polymerization activity was 10 kg · polymer / mmol Zr · hr. This polymer contained 11.0 mol% of units derived from 1-butene. The intrinsic viscosity [η] was 1.74 dl / g, and the melting point was 105.1 ° C. The percentage of heterogeneous bonds based on the 2,1-insertion was about 0.86%. Table 3 shows the physical properties measured for the obtained polymer.
[0195]
【Example4]
A 2-liter autoclave sufficiently purged with nitrogen was charged with 950 ml of hexane and 130 g of 1-butene, and 1 mmol of triisobutylaluminum was added. After heating to 70 ° C., propylene was supplied to supply a total pressure of 14 kg / cm.^TwoG, 0.30 mmol of methylaluminoxane, rac-dimethylsilylene-bis (2-methyl-4,6-diisopropyl-1-indenyl) zirconium dichloride produced in Production Example 2 was converted to Zr atom at 0.002. Mmol, and continuously supply propylene to increase the total pressure to 14 kg / cm.^TwoThe polymerization was carried out for 60 minutes while maintaining at G.
[0196]
After the polymerization, the polymer was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours.
The obtained polymer (propylene-based elastomer) was 10.1 g, and the polymerization activity was 5 kg · polymer / mmol Zr · hr. This polymer contained 15 mol% of units derived from 1-butene. The intrinsic viscosity [η] was 1.52 dl / g, and the melting point was 91.0 ° C. The percentage of heterogeneous bonds based on the 2,1-insertion was about 0.88%.
[0197]
Table 3 shows the physical properties measured for the obtained polymer.
[0198]
[Table 3]

Claims (3)

(1) a unit derived from propylene in an amount of 70 to 90 mol%, a unit derived from 1-butene in an amount of 10 to 30 mol%,
(2) (i) three head-to-tail linked propylene units, or
(ii) head - consists of a tail enchained propylene units and butene units and the side-chain methyl of the second unit of propylene units of propylene-butene-3 in the chain containing the second unit to the propylene units ¹³ C- NMR spectrum (based on hexachlorobutadiene solution and tetramethylsilane) was measured, and the total area of peaks at 19.5 to 21.9 ppm was defined as 100%, and the area of peaks at 21.0 to 21.9 ppm was determined. Is 90% or more,
(3) the intrinsic viscosity measured in decalin at 135 ° C. is 0.1 to 12 dl / g;
(4) the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 3 or less;
(5) The parameter B value indicating the randomness of the copolymer monomer chain distribution is 1.0 to 1.3,
(6) The melting point Tm measured by a differential scanning calorimeter is 60 to 105.1 ° C. , and the relationship between the melting point Tm and the 1-butene structural unit content M (mol%) is as follows:
−2.6M + 125 ≦ Tm ≦ −2.6M + 145,
(7) The relationship between the crystallinity C measured by the X-ray diffraction method and the 1-butene structural unit content M (mol%) is as follows:
C ≧ −1.5M + 65
A sealant characterized by comprising a propylene-based elastomer. The propylene-based elastomer,
[A] a metallocene compound represented by the following general formula [I] or [ II ] ,
[B] [B-1] an organoaluminum oxy compound, and / or
[B-2] a compound which reacts with the metallocene compound [A] to form an ion pair;
Optionally, in the presence of a catalyst for olefin polymerization containing [C] an organoaluminum compound,
The sealant according to claim 1, which is obtained by copolymerizing propylene and 1-butene;
Wherein, M is the Periodic Table IV B, VB, a transition metal of group VI B,
R ¹¹ and R ¹² may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, and an oxygen-containing group. Group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group,
R ¹³ and R ¹⁴ may be the same or different from each other, and are an alkyl group or an aryl group having 1 to 20 carbon atoms;
X ¹ and X ² may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, or a sulfur-containing group. Group,
Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O-,- CO -, - S -, - SO -, - SO 2 -, - NR 7 -, - P (R 7) -, - P (O) (R 7) -, - BR 7 - or -AlR ⁷ - ( Here, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms). ],
Wherein, M is a transition metal of IV B periodic table,
R ²¹ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, an optionally halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms , -NR ₂ , -SR , -OSiR _3, -SiR ₃ or -PR ₂ radicals (wherein R is a halogen atom, an alkyl group or an aryl group having 6 to 10 carbon atoms having 1 to 10 carbon atoms), and
R ^{22 to} R ²⁸ may be the same as R ²¹ described above , or an adjacent R ^{22 to} R ²⁸ may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded,
X ³ and X ⁴ may be the same or different from each other, and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, 10, an aryloxy group, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an OH group, or a halogen atom And
-Sn -, - O -, - S -, = SO, = SO 2, = NR 29, = CO, a = PR ²⁹ or = P (O) R ^29. (However, R ²⁹ and R ³⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, and an aryl having 6 to 10 carbon atoms. Group, C6-C10 fluoroaryl group, C1-C10 alkoxy group, C2-C10 alkenyl group, C7-C40 arylalkyl group, C8-C40 arylalkenyl group or It may be an alkylaryl group having 7 to 40 carbon atoms, or R ²⁹ and R ³⁰ may form a ring together with their bonding atoms, and M ² is silicon, germanium or tin.) . 3. The sealant according to claim 2, wherein the metallocene compound [A] is represented by the formula [I].