JP3350643B2 - Crystalline polypropylene - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a high melt tension,
The present invention relates to a crystalline polypropylene having excellent moldability, and more particularly, to a crystalline polypropylene suitable for blow molding and sheet molding.

[0002]

2. Description of the Related Art Polymers used for sheet, blow molding and the like are required to have a high melt tension, and for that purpose, a wide molecular weight distribution has been required. Therefore, conventionally, a TiCl ₃ -based catalyst has been used to produce a polymer having a high melt tension. However, the use of TiCl ₃ -based catalysts has problems that the activity is generally low and the rigidity of the product is not sufficiently high due to poor stereoregularity. Therefore, in order to solve these problems, various studies have been made on MgCl ₂ -supported catalysts capable of producing polypropylene having high activity and high stereoregularity. However, the molecular weight distribution is narrower than that of the TiCl ₃ -based catalyst, and the melt tension is not sufficiently high. Therefore, for a molding method requiring a high melt tension such as blow or sheet, the polymer produced by the MgCl ₂ -supported catalyst has not been an optimal polymer design.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and to provide an optimum polypropylene for blow and sheet having specific physical properties showing high melt tension. Is what you do.

[0004]

The present invention has been found to be able to solve the above-mentioned problems by providing a polypropylene having specific physical properties so as to have a high melt tension. That is, the polypropylene of the present invention provides a crystalline polypropylene characterized by having the following physical property values.

(1) The melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg is 0.1 to 100.
0 g / 10 min. (2) Amount dissolved in xylene at 23 ° C (CXS)
(3) The main endothermic peak temperature (Tmp) of the melting curve measured by a differential scanning calorimeter (DSC) is 163 ° C. or more. (4) Isotacticity measured by ¹³ C-NMR Pentad fraction (mmmm) is 96.0 or more. (5) Mz / Mn measured by GPC is 20.0 or more.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION
FR (melt flow rate) is generally 0.1 to 1
000 (g / 10 min.), Preferably 0.5 to 50 (g / 10 mi) in sheet and blow molding.
n. ) Can be preferably used. MFR is 0.1
If it is less than (g / 10 min.), The melt viscosity during molding generally increases, and the back pressure of the molding machine increases, which is not preferable.

On the other hand, if it exceeds 1000 (g / 10 min), the melt tension is reduced, and molding becomes difficult. Although the xylene dissolution amount (CXS) is within a range of 5.0% by weight or less,
Preferably it is 2.0% by weight or less. 5% by weight of CXS
If it exceeds, the molding surface becomes sticky and the commercial value is impaired.

The main endothermic peak temperature (Tmp) of the melting curve of the differential scanning calorimeter (DSC) is in the range of 163 ° C. or more, preferably 164 ° C. or more. If the temperature is lower than 163 ° C., heat resistance, which is a characteristic of polypropylene, is undesirably reduced. The isotactic pentad fraction (mmmm) measured by ¹³ C-NMR is in the range of 96.0 wt% or more, preferably 96.5 wt% or more. If the isotactic pentad fraction is less than 96.0, the crystallinity of the product is lowered and the rigidity is lowered, which is not preferable.

The Z-average molecular weight measured by GPC and n
The average molecular weight ratio (Mz / Mn) is preferably 20 or more. The grounds for such a definition are as follows. Conventionally, it is said that a wide molecular weight distribution is required to improve the moldability, and a Q value (Mw / Mn) measured by GPC is used as an index for the distribution. However, there is a problem that the Q value does not necessarily correlate with the moldability when the Q value is displayed.

In the present invention, as a result of examining the melt tension and the moldability, it is important that the molecular weight distribution spread to the high molecular weight side in order to give a high melt tension.
It has been found that by using a crystalline polypropylene having an n value, the melt tension is high and the moldability is excellent.

When Mz / Mn is 20 or less, a relatively high molecular weight component is insufficient, and when a sheet or blow molding is performed, a sufficient melt tension cannot be obtained, resulting in poor moldability.
The crystalline polypropylene of the present invention can be produced by any method as long as the desired polypropylene of the present invention can be obtained.

<Catalyst for Olefin Polymerization> The catalyst which can be used in the present invention is a combination of the components (A), (B) and (C). Here, “combined” does not mean that the components are only those listed (ie, only the components (A), (B) and (C)), but does not mean that the effects of the present invention can be obtained. Does not exclude coexistence of other components within a range not to impair the above.

(1) Solid catalyst component The component (A) is a contact product of a specific solid component (component (A1)) and a specific silicon compound (component (A2)). Such a component (A) of the present invention does not exclude the purposeful coexistence of other components other than the above essential two components.

Component (A1) The solid component used in the present invention is a solid component for stereoregular polymerization of propylene containing titanium, magnesium and halogen as essential components. Here, "containing as an essential component" means that besides the three components listed, it may contain other purposeful elements, and each of these elements exists as a purposeful arbitrary compound And that these elements may be present as bonded to each other.

The magnesium compound used as a magnesium source in the present invention includes magnesium dihalide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate and the like. Is mentioned. Among them, Mg (OR ⁶ ) z-pXp (here, R
⁶ is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, X represents a halogen, and p is 0 ≦ p ≦ 2. ) Is preferred.

The titanium compound serving as a titanium source is represented by the general formula Ti (OR ⁷ ) ₄ -qXq (where R ⁷ is a hydrocarbon group, preferably about 1 to 10 carbon atoms, and X is a halogen atom. And q is 0 ≦ q ≦ 4).

As a specific example, TiCl_Four, TiB
r_Four, Ti (OC_TwoH_Five) Cl_Three, Ti (OC_TwoH_Five)
_TwoCl_Two, Ti (OC_TwoH_Five)_ThreeCl, Ti (O-is
o-C_ThreeH₇) Cl_Three, Ti (On-C_FourH₉) Cl
_Three, Ti (On-C_FourH₉)_TwoCl_Two, Ti (OC_Two
H_Five) Br_Three, Ti (OC_TwoH_Five) (On-C)
_FourH₉) _TwoCl, Ti (On-C_FourH₉)_ThreeCl, T
i (OC₆H_Five) Cl_Three, Ti (O-iso-C
_FourH₉)_TwoCl_Two, Ti (On-C_FiveH₁₁) Cl_Three,
Ti (On-C₆H_Three) Cl_Three, Ti (OC_TwoH_Five)
_Four, Ti (On-C_ThreeH₇)_Four, Ti (On-C_Four
H₉)_Four, Ti (O-iso-C_FourH₉)_Four, Ti (O
-N-C₆H₁₃)_Four, Ti (On-C₈H₁₇)_Four,
Ti (OCH_TwoCH (C_TwoH_Five) C_FourH₉)_FourEtc.
Can be

Further, TiX '_Four(Where X 'is a halogen
It is. ) By reacting with an electron donor described later
The compound can also be used as a titanium source. like that
Specific examples of the molecular compound include TiCl_Four・ CH_ThreeCO
C_TwoH_Five, TiCl_Four・ CH _ThreeCO_TwoC_TwoH_Five, TiC
l_Four・ C₆H_FiveNO_Two, TiCl_Four・ CH_ThreeCOCl,
TiCl_Four・ C₆H_FiveCOCl, TiCl_Four・ C₆H_Five
CO_TwoC_TwoH_Five, TiCl_Four・ ClCOC_TwoH_Five, Ti
Cl_Four・ C_FourH_FourO and the like.

TiCl ₃ (including those obtained by reducing TiCl ₄ with hydrogen, those reduced with aluminum metal, or those reduced with an organometallic compound), TiBr
_{3, Ti (OC 2 H 5} ) Cl 2, TiCl 2, the use of dicyclopentadienyl titanium dichloride, cyclopentadienyl titanium trichloride titanium compounds such as chloride are also possible. Among these titanium compounds, Ti
Cl ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (OC ₂ H)
₅ ) Cl ₃ is preferred.

The halogen is usually supplied from the above-mentioned halides of magnesium and / or titanium, but may be other halogen sources, for example aluminum halides such as AlCl ₃ or silicon halides such as SiCl _4. Halide, phosphorus halide such as PCl ₃ , PCl ₅ , tungsten halide such as WCl ₆ , MO
It can be supplied from a known halogenating agent such as a halide of molybdenum such as Cl ₅ . The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred.

The solid components used in the present invention include Al (OC ₂ H ₅ ) ₃ and Al (O-iso-C ₃ ) in addition to the above essential components.
H ₇ ) ₃ , aluminum compounds such as Al (OCH ₃ ) ₂ Cl, and B (OCH ₃ ) ₃ , B (OC ₂ H ₅ ) ₃ , B
It is also possible to use a boron compound such as (OC ₆ H ₅ ) ₃ and other components, and these may remain in the solid component as components such as aluminum and boron.

Further, when producing this solid component,
It can also be prepared using an electron donor as an internal donor. Electron donors (internal donors) that can be used in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides,
Examples thereof include oxygen-containing electron donors such as acid anhydrides, and nitrogen-containing electron donors such as ammonia, amine, nitrile, and isocyanate.

More specifically, (a) a compound having 1 to 18 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol and isopropylbenzyl alcohol; Alcohols, (b) phenol, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol,
C6 to C2 which may have an alkyl group such as naphthol
5 phenols, (c) ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc. Aldehydes having 2 to 15 carbon atoms, (e)
Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate Ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, Ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone, α-valerolactone, coumarin, phthalidone organic acid monoester, Or diethyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate, ethylene carbonate, norbornanedienyl-1,2-dimethylcarboxylate, Organic acid esters having 2 to 20 carbon atoms, such as organic acid polyvalent esters such as cyclopropane-1,2-dicarboxylic acid-n-hexyl and diethyl 1,1-cyclobutanedicarboxylate, (f) ethyl silicate, silicic acid Inorganic acid esters such as silicate esters such as butyl and phenyltriethoxysilane;
Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, and phthaloyl isochloride;
(H) ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; ,
(Nu) methylamine, ethylamine, diethylamine,
Tributylamine, piperidine, tribenzylamine,
Amines such as aniline, pyridine, picoline, tetramethylethylenediamine, nitriles such as (ル) acetonitrile, benzonitrile, tolunitrile, (ヲ) 2
-(Ethoxymethyl) -ethyl benzoate, 2- (t-butoxymethyl) -ethyl benzoate, 3-ethoxy-2-
Alkoxy ester compounds such as ethyl phenylpropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxy-2-S-butylpropionate and ethyl 3-ethoxy-2-t-butylpropionate; (W) 2-benzoyl Examples thereof include ketoester compounds such as ethyl benzoate, ethyl 2- (4'-methylbenzoyl) benzoate and ethyl 2-benzoyl-4,5-dimethylbenzoate. Two or more of these electron donors can be used. Among these, organic acid ester compounds and acid halide compounds are preferred, and phthalic acid diester compounds, cellosolve acetate compounds and phthalic acid dihalide compounds are particularly preferred.

Component (A2) The silicon compound used in the present invention has the general formula R ¹ R ² S
i (OC ₂ H ₅ ) ₂ (where R ¹ is a branched aliphatic hydrocarbon group or a cycloaliphatic hydrocarbon group, and R ² is the same or different hydrocarbon group or hetero atom-containing hydrocarbon group as R ¹⁾ .). Where R
^{When 1} is a branched aliphatic hydrocarbon group, those branched from a carbon atom adjacent to a silicon atom are preferred. In this case, the branching group is preferably an alkyl group, a cycloalkyl group, or an aryl group (for example, a phenyl group or a methyl-substituted phenyl group). More preferred R ¹
Is a carbon atom adjacent to a silicon atom, that is, the carbon atom at the α-position is a secondary or tertiary carbon atom.
In particular, those having a tertiary carbon atom bonded to a silicon atom are preferred. When R ¹ is a branched hydrocarbon group, the number of carbon atoms is usually 3 to 20, preferably 4 to 10. When R ¹ is a cycloaliphatic hydrocarbon group, the number of carbon atoms is usually 4 to 20, preferably 5 to 10. R ² is R ¹
And the same or different hydrocarbon group or hetero atom-containing hydrocarbon group is preferable, and is a hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms or a hetero atom-containing hydrocarbon group. Specific examples of the silicon compound that can be used in the present invention are as follows.

(Tert-C_FourH₉) Si (CH_Three)
(OC_TwoH_Five)_Two, (Tert-C_FourH₉) Si (C_Two
H_Five) (OC_TwoH_Five)_Two, (Tert-C_FourH₉) Si
(N-C_ThreeH₇) (OC_TwoH_Five)_Two, (Tert-C_Four
H₉) Si (iso-C)_ThreeH₇) (OC_TwoH_Five)_Two,
(Tert-C_FourH₉) Si (n-C_FourH₉) (OC_Two
H _Five)_Two, (Tert-C_FourH₉) Si (iso-C)_Four
H₉) (OC_TwoH_Five)_Two, (Tert-C_FourH₉) Si
(Sec-C_FourH₉) (OC_TwoH_Five)_Two, (Tert-
C_FourH₉) Si (tert-C_FourH₉) (OC_TwoH_Five)
_Two, (Tert-C _FourH₉) Si (n-C_FiveH₁₁) (O
C_TwoH_Five)_Two, (Tert-C_FourH₉) Si (cycl)
o-C_FiveH₉) (OC_TwoH_Five)_Two, (Tert-C_FourH
₉) Si (n-C₆H₁₃) (OC_TwoH_Five)_Two, (Ter
t-C_FourH₉) Si (cyclo-C) ₆H₁₁) (OC_Two
H_Five)_Two, (Tert-C_FourH₉) Si (On-C_Three
H₇) (OC_TwoH_Five)_Two, (Tert-C_FourH₉) Si
(O-iso-C_ThreeH₇) (OC_TwoH_Five)_Two, (Ter
t-C_FourH₉) Si (On-C_FourH₉) (OC
_TwoH_Five)_Two, (Tert-C_FourH₉) Si (O-iso
-C_FourH₉) (OC_TwoH_Five)_Two, (Tert-C
_FourH₉) Si (O-sec-C_FourH₉) (OC_TwoH_Five)
_Two, (Tert-C_FourH₉) Si (O-tert-C_Four
H₉) (OC_TwoH_Five)_Two, (Tert-C_FourH₉) Si
(On-C_FiveH₁₁) (OC_TwoH_Five)_Two, (Tert-
C_FourH₉) Si (O-cyclo-C)_FiveH₉) (OC_Two
H_Five)_Two, (Tert-C_FourH₉) Si (On-C₆
H₁₃) (OC_TwoH_Five)_Two, (Tert-C_FourH₉) Si
(O-cyclo-C₆H₁₁) (OC_TwoH_Five)_Two, (I
so-C_ThreeH₇) _TwoSi (OC_TwoH_Five)_Two, (Iso-
C_FourH₉)_TwoSi (OC_TwoH_Five)_Two, (Sec-C_FourH
₉)_TwoSi (OC_TwoH_Five)_Two, (Neo-C_FiveH₁₁)_Two
Si (OC _TwoH_Five)_Two, (Cyclo-C_FiveH₉)_TwoS
i (OC_TwoH_Five)_Two, (Cyclo-C₆H₁₁) Si
(CH_Three) (OC_TwoH_Five)_Two, (Cyclo-C
₆H₁₁) Si (C_TwoH_Five) (OC_TwoH_Five)_Two, (Cyc
lo-C₆H₁₁) Si (n-C_FourH₉) (OC_TwoH_Five)
_Two, (Cyclo-C₆H₁₁) Si (cyclo-C)_Five
H₉) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (CH
_Three) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (C_TwoH
_Five) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (n-C
_ThreeH₇) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (i
so-C_ThreeH₇) (OC _TwoH_Five)_Two, (C_TwoH_Five)_ThreeC
Si (n-C_FourH₉) (OC_TwoH_Five)_Two, (C_TwoH_Five)
_ThreeCSi (iso-C_FourH₉) (OC_TwoH_Five)_Two, (C
_TwoH_Five)_ThreeCSi (sec-C_FourH₉) (OC_TwoH_Five)
_Two, (C_TwoH_Five)_ThreeCSi (tert-C _FourH₉) (O
C_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (n-C_FiveH₁₁)
(OC_TwoH _Five)_Two, (C_TwoH_Five)_ThreeCSi (cyclo
-C_FiveH₉) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi
(N-C₆H₁₃) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeC
Si (cyclo-C₆H₁₁) (OC_TwoH_Five)_Two, H
(CH_Three)_TwoC (CH_Three)_TwoCSi (CH_Three) (OC_Two
H_Five)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi (C_Two
H_Five) (OC_TwoH_Five)_Two, H (CH_Three)_TwoC (CH_Three)
_TwoCSi (n-C_ThreeH₇) (OC_TwoH_Five)_Two, H (CH
_Three)_TwoC (CH_Three)_TwoCSi (iso-C_ThreeH₇) (O
C_TwoH_Five)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi
(N-C_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_Two(C
_TwoH_Five) CSi (CH_Three) (OC_TwoH_Five)_Two, (Ter
t-C_FourH₉) Si (OC_TwoH_Five)_Three(CH_Three)_Two(C
_TwoH_Five) CSi (OC_TwoH_Five)_Three, (CH_Three) (C_TwoH
_Five)_TwoCSi (OC_TwoH_Five)_Three, H (CH_Three)_TwoC (C
H_Three)_TwoCSi (OC_TwoH_Five)_Three, (Norbornyl) S
i (CH_Three) (OC_TwoH_Five)_Two, (Norbornyl) Si
(OC_TwoH_Five)_Three, (Adamantyl) Si (OC
_TwoH_Five)_Three, (Adamantyl) Si (CH_Three) (OC_Two
H_Five) _TwoAnd the like.

Further, as described above, in the production of the component (A) of the present invention, an optional component may be contained as necessary in addition to the above-mentioned essential component. Suitable compounds include the following compounds.

(A) Vinyl silane compound As the vinyl silane compound, monosilane (SiH ₄ )
At least one hydrogen atom is a vinyl group (CH ₂ ＣC
H-), and some of the remaining hydrogen atoms are halogen (preferably Cl), alkyl groups (preferably hydrocarbon groups having 1 to 12 carbon atoms), aryl groups (preferably phenyl), alkoxy groups (Preferably an alkoxy group having 1 to 12 carbon atoms) and a structure substituted with others.

More specifically, CH ₂ ＣＨCH—Si
_{H 3, CH 2 = CH-} SiH 2 (CH 3), CH 2 = C
_{H-SiH (CH 3) 2} , CH 2 = CH-Si (C 2 H
₅ ) ₃ , CH ₂ ＣＨCH—Si (CH ₃ ) ₂ (C
_{2 H 5), CH 2 =} CH-Si (CH 3) (C 2 H 5)
_{2, CH 2 = CH-Si} (n-C 4 H 9), CH 2 = C
_{H-Si (C 6 H 5} ) 3, CH 2 = CH-Si (C
_{H 3) (C 6 H 5} ) 2, CH 2 = CH-Si (CH 3)
₂ (C ₆ H ₅ ), CH ₂ ＣＨCH—Si (CH ₃ ) ₂ (C
_{6 H 4 CH 3), (} CH 2 = CH) (CH 3) 2 Si-
_{O-Si (CH 3) 2} (CH = CH 2), (CH 2 = C
H) ₂ SiH ₂ , (CH ₂ ＣＨCH) ₂ Si (C
H _{3) 2,} can be exemplified _{(CH 2 = CH) 2 Si} (C 6 H 5) 2 and the like.

(B) Organometallic compounds of metals of groups I to III of the periodic table It is also possible to use organometallic compounds of metals of groups I to III of the periodic table. Periodic Table I used in the present invention
The organometallic compounds of Group III-III metals have at least one organic group-metal bond. As the organic group in that case, a hydrocarbyl group having about 1 to 20 carbon atoms, preferably about 1 to 6 carbon atoms is representative. In an organometallic compound where at least one of the valences is filled with an organic group, the remaining valences of the metal (if any) are hydrogen, halogen, hydrocarbyloxy (hydrocarbyl is
Is satisfied by) other - C20 about atoms, preferably (specifically, -O-Al (CH ₃ in the case of methyl alumoxane) the metal through the 1-6 degree), or oxygen atom .

Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium, and tert-butyllithium, (b) butylethylmagnesium, dibutylmagnesium, and hexylethylmagnesium. , Butylmagnesium chloride, organic magnesium compounds such as tert-butylmagnesium bromide, (c) organic zinc compounds such as diethyl zinc and dibutyl zinc, (d) trimethylaluminum, triethylaluminum, triisobutylaluminum,
There are organic aluminum compounds such as tri-n-hexylaluminum, diethylaluminum chloride, diethylaluminum hydride, diethylaluminum ethoxide, ethylaluminum sesquichloride, ethylaluminum dichloride and methylalumoxane. Of these, organoaluminum compounds are particularly preferred.

The above optional components (a) and (b) can be used alone or in combination of two or more.
When these optional components are used, the effect of the present invention is further increased.

Production of Component (A) Component (A) is prepared by bringing the components constituting component (A) or, if necessary, the above-mentioned optional components into contact with each other in a stepwise or temporary manner to form an intermediate and / or intermediate component. Alternatively, it can be produced by finally washing with an organic solvent such as a hydrocarbon solvent or a halogenated hydrocarbon solvent.

In this case, a solid product containing titanium, magnesium and halogen as essential components is first produced, and the solid product is brought into contact with a silicon compound of the above general formula (a two-step method). In the process of producing a solid product containing magnesium, halogen and halogen as essential components, it is also possible to employ a method of producing the component (A) at a stroke (in other words, a one-step method) by making the silicon compound already exist. The preferred scheme is the former.

The conditions for contacting the components constituting the component (A) may be any conditions as long as the effects of the present invention are recognized, but the following conditions are generally preferred. The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C.
It is. Examples of the contacting method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring / pulverizing machine, and a method of bringing into contact by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, and polysiloxanes.

The ratio of the amounts of the respective components constituting the component (A) can be arbitrary as long as the effects of the present invention are recognized, but generally, the following ranges are preferable. The amount of the titanium compound used is preferably in the range of 0.0001 to 1000, and more preferably in the range of 0.01 to 10 as a molar ratio to the amount of the magnesium compound used. When a compound for that purpose is used as a halogen source, the amount of the compound used may be 0.01 mol ratio to the amount of magnesium used, regardless of whether the titanium compound and / or the magnesium compound contains halogen or not. ~ 1
000, preferably 0.1 to 100. The amount of the silicon compound used as the component (A2) is
The atomic ratio (Si / Ti) of silicon to the titanium component constituting the component (A) is in the range of 0.01 to 1000, preferably 0.1 to 100.

When the vinylsilane compound is used, the amount of the vinylsilane compound to be used is m with respect to the titanium component constituting the component (A).
The ol ratio is preferably in the range of 0.001 to 1000, and more preferably 0.01 to 100. When the aluminum and boron compounds are used, the amount of the aluminum compound and the boron compound is 0.1 mol per mol of the above-mentioned magnesium compound.
It is preferably in the range of 001 to 100, preferably 0.01 to 100.
Within the range of 1. When the electron donor is used, the amount used is m with respect to the amount of the magnesium compound.
The ol ratio is preferably in the range of 0.001 to 10, and more preferably in the range of 0.01 to 5.

The component (A) is produced by contacting the component (A1) with the component (A2) and optionally using other components such as an electron donor, for example, by the following production method. (A) A method in which a magnesium halide is brought into contact with an electron donor, a titanium-containing compound, a silicon compound and a sulfonate compound as required.

(B) A method in which alumina or magnesia is treated with a phosphorus halide compound and brought into contact with a magnesium halide, an electron donor, a silicon compound, a titanium halide-containing compound and a sulfonic acid ester compound.

(C) A reaction product obtained by contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound is inert. After washing with an organic solvent, a method of contacting a silicon compound with a sulfonic acid ester compound or separately contacting each other. As the polymer silicon compound, a compound represented by the following formula is suitable.

[0040]

Embedded image

(Here, R ⁸ is a hydrocarbon group having about 1 to 10 carbon atoms, and r represents a degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 cSt.)
Specifically, methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7 And 9-pentamethylcyclopentasiloxane are preferred.

(D) A magnesium compound is dissolved with a titanium tetraalkoxide and / or an electron donor, and a silicon compound, a titanium compound and a sulfonic acid ester compound are added to a solid component precipitated with a halogenating agent or a titanium halide compound. A method of contacting or contacting each separately.

(E) After reacting an organomagnesium compound such as a Grignard reagent with a halogenating agent, a reducing agent and the like,
A method in which an electron donor is brought into contact with this, if necessary, and then a silicon compound, a titanium compound and a sulfonic acid ester compound are brought into contact with each other, or they are separately brought into contact with each other.

(F) A method in which a halogenating agent and / or a titanium compound, a silicon compound and a sulfonic acid ester compound are brought into contact with an alkoxymagnesium compound in the presence or absence of an electron donor or separately.

Among these production methods, (a) and (c)
(D) and (f) are preferred. Component (A) is used during and / or at the end of its preparation in an inert organic solvent, such as an aliphatic or aromatic hydrocarbon solvent (eg hexane, heptane, toluene, cyclohexane, etc.), or a halogenated hydrocarbon solvent ( For example, n-butyl chloride,
(1,2-dichloroethylene, carbon tetrachloride chlorobenzene, etc.).

Component (A) can also be used after a prepolymerization step comprising contacting and polymerizing a vinyl group-containing compound such as an olefin, a diene compound, or styrene. Specific examples of the olefins used in performing the prepolymerization include, for example, those having 2 to 2 carbon atoms.
About 20; specifically, ethylene, propylene,
-Butene, 3-methylbutene-1, 1-pentene, 1-
Hexene, 4-methylpentene-1, 1-octene, 1
-Decene, 1-undecene, 1-eicosene and the like,
Specific examples of the diene compound include 1,3-butadiene,
Isoprene, 1,4-hexadiene, 1,5-hexadiene, 1,3-pentadiene, 1,4-pentadiene,
2,4-pentadiene, 2,6-octadiene, cis
-2, trans-4-hexadiene, trans-
2, trans-4-hexadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene,
1,6-heptadiene, 2,4-heptadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4
-Cyclohexadiene, cyclopentadiene, 1,3-
Cycloheptadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,9-decadiene, 1,13-tetradecadiene, p-divinylbenzene, m-divinylbenzene, O- Examples include divinylbenzene and dicyclopentadiene. Specific examples of styrenes include styrene, α-methylstyrene, allylbenzene, chlorostyrene, and the like.

The reaction conditions of the titanium component and the vinyl group-containing compound may be any conditions, but generally, the following ranges are preferable. The prepolymerization amount of the vinyl group-containing compound is 0.001 to 100 g per 1 g of titanium solid component,
Preferably 0.1 to 50 g, more preferably 0.5 to
It is in the range of 10 g. The reaction temperature during prepolymerization is -15
The temperature is 0 to 150 ° C, preferably 0 to 100 ° C. A polymerization temperature that is lower than the “main polymerization”, that is, the polymerization temperature when the α-olefin is polymerized, is preferable. The reaction is
Generally, it is preferable to perform the reaction with stirring, and at that time, an inert solvent such as n-hexane or n-heptane may be present.

[0048] (2) Specific examples of the organoaluminum compound component an organoaluminum compound component (Component _{^{(B)), R 9 3}} - s AlX s or R ¹⁰ ₃ - _t Al (OR
¹¹ ) _t (where R ⁹ and R ¹⁰ are a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms, R ¹¹ is a hydrocarbon group, X is a halogen, and s and t are each 0 ≦ s
<3, 0 <t <3. ). Specific examples include (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n
-Alkyl aluminum halides such as trialkylaluminum such as hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride; (C) Alkyl aluminum hydride such as diethyl aluminum hydride, diisobutyl aluminum hydride donor, and (d) alkyl aluminum alkoxide such as diethyl aluminum ethoxide and diethyl aluminum phenoxy donor.

[0049] These (a) to other organometallic compound with an organoaluminum compound (d), for example R ¹² ₃ - _u Al
(OR ¹³ ) _u (where R ¹² and R ¹³ are the same or different and are a hydrocarbon group having 1 to 20 carbon atoms, and u is 0 <u ≦ 3). Alkoxides can also be used in combination. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum and diethylaluminum ethoxide and diethylaluminum monochloride And the like. The ratio of the organoaluminum compound component (B) to the titanium component in the solid catalyst component (A) is generally Al / Ti = 1 to 1000 mol / mol, preferably Al / Ti = 10 ~ 500m
ol / mol.

(3) Silicon compound component The silicon compound component (C) is a silicon compound represented by the following general formula:

[0051]

Embedded image

Compounds are preferably used.

(Where R ³ is an alicyclic or branched hydrocarbon group having 3 to 10 carbon atoms and a secondary or tertiary carbon atom adjacent to the Si atom, and R ⁴ is a C 1 to C 10 carbon atom) , R ⁵ is an aliphatic hydrocarbon group having 2 to 15 carbon atoms, and R ⁴ has 1 or more carbon atoms than R ^5. )

Specific examples of the silicon compound usable in the present invention
Is as follows. (Tert-C_FourH₉) (Se
c-C_FourH₉) Si (OCH_Three)_Two, (Tert-C_Four
H₉) (2-C_FiveH₁₁) Si (OCH_Three)_Two, (Ter
t-C_FourH₉) (3-C₆H₁₃) Si (OCH_Three)_Two,
(Cyclo-C_FiveH₉) (Sec-C _FourH₉) Si
(OCH_Three)_Two, (Cyclo-C_FiveH₉) (2-C_Five
H₁₁) Si (OCH_Three)_Two, (Cyclo-C_FiveH₉)
(3-C₆H₁₃) Si (OCH_Three) _Two, (CH_Three-Cy
clo-C_FiveH₉) (Sec-C_FourH₉) Si (OCH
_Three) _Two, (CH_Three-Cyclo-C_FiveH₉) (2-C_Five
H₁₁) Si (OCH_Three)_Two, (CH_Three-Cyclo-C
_FiveH₉) (3-C₆H₁₃) Si (OCH_Three)_Two, (Cy
clo-C₆H₁₁) (Sec-C_FourH₉) Si (OCH
_Three)_Two, (Cyclo-C₆H₁₁) (2-C_FiveH₁₁) S
i (OCH_Three)_Two, (Cyclo-C₆H₁₁) (3-C
₆H₁₃) Si (OCH_Three)_Two, (CH_Three-Cyclo-
C₆H₁₁) (Sec-C_FourH₉) Si (OCH_Three)_Two,
(CH_Three-Cyclo-C₆H₁₁) (2-C_FiveH₁₁) S
i (OCH_Three)_Two, (CH_Three-Cyclo-C₆H₁₁)
(3-C ₆H₁₃) Si (OCH_Three)_Two, Etc.
Can be.

Of these, preferred is (tert-
C_FourH₉) (Sec-C_FourH₉) Si (OCH_Three)_Two,
(Tert-C_FourH₉) (2-C_FiveH₁₁) Si (OCH
_Three)_Two, (Tert-C_FourH₉) (3-C₆H₁₃) Si
(OCH_Three)_Two, (Cyclo-C_FiveH₉) (Sec-
C _FourH₉) Si (OCH_Three)_Two, (Cyclo-C_FiveH
₉) (2-C_FiveH₁₁) Si (OCH_Three)_Two, (Cycl
o-C_FiveH₉) (3-C₆H₁₃) Si (OCH_Three) _Two,
And so on.

<Polymerization of Propylene> In the polymerization step of propylene, the components (A), (B) and (C) are fed to a polymerization system for polymerization. The ratio with respect to the titanium component may be arbitrary, but is preferably in the range of Si / Ti = 0.1 to 100, more preferably Si / Ti = 1 to 10.

The polymerization method for producing the crystalline polypropylene of the present invention may be any method as long as the target polypropylene of the present invention can be obtained, and examples thereof include the following methods. Examples thereof include slurry polymerization using a hydrocarbon solvent, liquid-phase solventless polymerization (bulk polymerization) substantially using no solvent, solution polymerization, and gas-phase polymerization.
As a polymerization solvent in the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon solvent such as pentane, hexane, heptane, cyclohexane, benzene, and toluene is used alone or as a mixture. Examples of the polymerization method employed include a method of performing continuous polymerization, batch polymerization, multistage polymerization, or prepolymerization. The polymerization temperature is usually 20 to 20
The polymerization pressure is about 0 ° C., preferably about 50 to 150 ° C., and the polymerization pressure is about atmospheric pressure to about 300 kg / cm ² , preferably about atmospheric pressure to 100 kg / cm ² , in which case hydrogen is used as a molecular weight regulator in an auxiliary manner. be able to.

In the polymerization using the catalyst system of the present invention, in addition to homopolymerization of propylene, copolymerization with a monomer copolymerizable with propylene (eg, ethylene, α-olefin, diene, styrene, etc.) is also performed. be able to. 15% by weight of these copolymerizable monomers in random copolymerization
Up to 50 wt% in block copolymerization.

[0059]

The present invention will be described in more detail with reference to the following examples. The method and apparatus for measuring each physical property value in the present invention are described below.

[MFR] Apparatus: Melt indexer manufactured by Takara Measuring method: JIS-K6758.

[CXS] Measurement method: A sample (about 5 g) was treated with xylene (30 g) at 140 ° C.
0 ml), cooled to 23 ° C. and allowed to stand for 12 hours, and then filtered. The filtrate was removed to recover the dissolved solid, and the weight ratio of the recovered solid was determined. I asked.

[Differential Scanning Calorimeter (DSC)] Apparatus: DSC-2 manufactured by PERKIN-ELCH3R Measurement method: A sample (about 5 mg) was melted at 200 ° C. for 3 minutes, and then melted at 10 ° C./min. After cooling to 30 ° C. at a rate of 10 ° C./min. The temperature was raised to 200 ° C. to obtain a melting curve, and a main endothermic peak temperature (Tmp) was determined.

[ ¹³ C-NMR] Apparatus: GSX-270 manufactured by JEOL Co., Ltd. Measurement method: Using o-dichlorobenzene / deuterated benzene solvent as a solvent at a measurement temperature of 130 ° C. by a proton decoupling method to obtain a total polymer The weight ratio of the mmmm component in the components was determined.

[Melt tension (MT)] Apparatus: Capillograph 1B manufactured by Toyo Seiki Seisaku-sho, Ltd. Measurement method: 10 mm / min. In a barrel heated to 190 ° C. and having an inner diameter of 9.55 mm. The melt tension was measured when extruding the molten polymer at a speed of 2.16 mm and pulling a strand coming out of an orifice having an inner diameter of 2.16 mm and a length of 8 mm at a speed of 4 mm / min.

Example 1 [Production of Component (A)] In a flask sufficiently purged with nitrogen,
200 ml of dehydrated and deoxygenated n-heptane were introduced, and then 0.4 mol of MgCl ₂ and Ti (On-
0.8 mol of O ₄ H ₉ ) ₄ was introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then methylhydropolysiloxane (of 20 cSt) was added for 48 hours.
ml, and reacted for 3 hours. The generated solid component is represented by n
-Washed with heptane.

Next, into a flask sufficiently purged with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced,
The solid component synthesized above was converted to 0.24 mo in terms of Mg atom.
1 was introduced. Then, SiCl ₄ was added to 25 ml of n-heptane.
0.4 mol was mixed, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, n-
Washed with heptane. Then, 0.024 mol of phthalic acid chloride was mixed with 25 ml of n-heptane,
The mixture was introduced into the flask at 30 ° C for 30 minutes and reacted at 90 ° C for 1 hour. After the completion of the reaction, the resultant was washed with n-heptane. Then, 0.4 mol of SiCl ₄ was introduced and reacted at 80 ° C. for 6 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a solid component for producing the component (A).

Next, into a flask sufficiently purged with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced,
5 g of the solid component synthesized above was introduced, and (tert-C
₄ H ₉ ) Si (CH ₃ ) (OC ₂ H ₅ ) ₂ 1.0 ml,
31.7 g of Al (C ₂ H ₅ ) was contacted at 30 ° C. for 2 hours. After the completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. This had a titanium content of 1.4 wt%.

[Polymerization of Propylene] Stirring and Temperature Control
1.51 stainless steel oak with internal volume
In the reave, fully dehydrated and deoxygenated n-heptane
500 ml, triethyl aluminum as component (B)
125 mg, as component (C) (tert-C_FourH ₉)
(Sec-C_FourH₉) Si (OCH_Three)_Two0.72mg
And 15 mg of the component (A) prepared above, and then water
Introduce 150 ml of nitrogen, raise the temperature and raise the pressure, polymerization pressure = 5 kg
/ Cm^TwoG, polymerization temperature = 75 ° C., polymerization time = 2 hours
Propylene was polymerized. After the polymerization is completed, the
The limer slurry is separated by filtration and the polymer is dried.
I let you. As a result, 155.6 g of a polymer was obtained.
From the filtrate, 0.63 g of polymer was obtained. Also
The obtained polymer had an MFR of 3.43 (g / 10 mi).
n. ), Xylene dissolved amount at 23 ° C. (CXS) = 1.42
(Wt%), peak temperature of melting curve by DSC (Tm
p) = 164.7 (° C.), isotacticity by NMR
Kupentad fraction (mmmm) = 96.7 (%), MT
= 4.3 g, Mz / Mn measured by GPC = 25.8
there were.

Example 2 As the component (C), (tert-C_FourH₉) (Sec-C
_FourH₉) Si (OCH _Three)_TwoUsing 3.6mg, hydrogen
Was carried out in the same manner as in Example 1 except that 345 ml of
Was. As a result, 176.1 g of a polymer was obtained.
0.61 g of polymer was obtained from the filtrate. Also
The obtained polymer had an MFR of 5.85 (g / 10 mi).
n. ), Xylene dissolved amount at 23 ° C. (CXS) = 0.83
(Wt%), peak temperature of melting curve by DSC (Tm
p) = 164.7 (° C.), isotacticity by NMR
Kupentad fraction (mmmm) = 96.7 (%), MT
= 4.1 g, Mz / Mn = 20.6 measured by GPC
there were.

Example 3 As a component ( A2 ), (cyclo-C ₆ H ₁₁ ) (C
H ₃₎ using _{Si (OC 2 H 5) 2} , 150m hydrogen
Polymerization was carried out in the same manner as in Example 2 except that l was introduced. As a result, 178.0 g of a polymer was obtained. 0.331 g of polymer was obtained from the filtrate. The obtained polymer had an MFR of 2.48 (g / 10 min.),
Dissolved amount of xylene at 23 ° C (CXS) = 1.20 (wt
%), Peak temperature of melting curve by DSC (Tmp) =
164.2 (° C.), isotactic pentad fraction (mmmm) by NMR = 96.5 (%), MT = 4.
8 g, Mz / Mn measured by GPC = 20.2.

Example 4 As the component ( A2 ), (cyclo-C ₆ H ₁₁ ) ₂ Si
Polymerization was carried out in the same manner as in Example 2 except that (OC ₂ H ₅ ) ₂ was used and 150 ml of hydrogen was introduced. As a result, 17
3.1 g of polymer were obtained. From the filtrate, 0.5
2 g of polymer were obtained .

The obtained polymer had an MFR of 1.6.
7 (g / 10 min.), Xylene dissolved amount at 23 ° C. (C
XS) = 1.40 (wt%), dissolution curve by DSC
Peak temperature (Tmp) = 164.0 (° C), by NMR
Isotactic pentad fraction (mmmm) = 9
6.6 (%), MT = 6.1 g, Mz measured by GPC
/Mn=21.0.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that 75 ml of hydrogen was introduced without using the component (C). As a result, 128.7
g of polymer were obtained. 1.00 g of polymer was obtained from the filtrate. The obtained polymer is MFR
= 2.47 (g / 10 min.), Xylene dissolved amount (CXS) at 23 ° C. = 2.99 (wt%), peak temperature of melting curve by DSC (Tmp) = 162.2 (° C.), N
Isotactic pentad fraction by MR (mmm
m) = 93.7 (%), MT = 2.8 g, Mz / Mn = 16.3 as measured by GPC.

Comparative Example 2 (tert-C ₄ H ₉ ) (CH ₃ ) S as Component (C)
The same polymerization as in Example 1 was carried out except that 0.72 mg of i (OCH ₃ ) ₂ was used. As a result, 151.4 g of a polymer was obtained. 0.74 g of polymer was obtained from the filtrate. The obtained polymer had MFR = 9.
61 (g / 10 min.), Xylene dissolution amount (CXS) at 23 ° C. = 1.99 (wt%), peak temperature (Tmp) of dissolution curve by DSC = 164.0 (° C.), NMR
Pentad fraction (mmmm) =
96.3 (%), MT = 3.7 g, M measured by GPC
z / Mn = 18.4.

Comparative Example 3 In the production of component (A), (tert-C_FourH₉) (C
H_Three) Si (OC_TwoH _Five)_TwoInstead of (tert-C
_FourH₉) (CH_Three) Si (OCH_Three)_TwoOther than using
Performed the same polymerization as in Comparative Example 1. As a result, 17
8.2 g of polymer were obtained. From the filtrate, 0.3
6 g of polymer were obtained. The obtained polymer is
MFR = 4.78 (g / 10 min.), 23 ° C.
Len dissolved amount (CXS) = 0.35 (wt%), DSC
Melting curve peak temperature (Tmp) = 165.0
(° C), isotactic pentad fraction by NMR
(Mmmm) = 97.2 (%), MT = 1.9 g, GP
Mz / Mn measured at C was 15.9.

[0076]

According to the present invention, a crystalline polypropylene having a high melt tension can be defined. In addition, since it is excellent in molding workability by using this, there is an effect that it can be optimally used for blow and sheet molding.

──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/00-4/82 C08F 10/00-10/14 C08F 110/00-110/14 C08F 210 / 00-210/18

Claims (3)

(57) [Claims] 1. A crystalline polypropylene having the following physical properties. (1) The melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg is 0.1 to 1000 g / 10 m
in. (2) Amount dissolved in xylene at 23 ° C (CXS)
0.83% by weight or more and 5.0% by weight or less (3) The main endothermic peak temperature (Tmp) of the melting curve measured by a differential scanning calorimeter (DSC) is 163 ° C. or more ,
164.7 ° C. or less (4) The isotactic pentad fraction (mmmm) measured by ¹³ C-NMR is 96.0 % by weight or more and 96.
7 wt% or less (5) Mz / Mn, measured by GPC, 20.0 or more,
25.8 or less 2. A main endothermic peak temperature (Tmp) of a melting curve measured by a differential scanning calorimeter (DSC) is 164 ° C.
The crystalline polypropylene according to claim 1, which is the above. 3. The crystalline polypropylene according to claim 1, wherein the isotactic pentad fraction (mmmm) measured by ¹³ C-NMR is 96.5% by weight or more.