JPH06240069A - Propylene resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent mechanical properties over a wide range of modulus and small temperature dependency of mechanical properties and giving a nonsticky molded surface. CONSTITUTION:This resin composition comprises 10-95wt.% propylene homopolymer and/or propylene copolymer containing at most 4mol% units of another olefin each of which has an intrinsic viscosity [eta] of 0.5-10dl/g in decalin at 135 deg.C and a content (W) of boiling n-heptane insolubles of 10-99wt.% and satisfies the relationships: T2HR (80)<=670-2.2XW and T2HR (80)/T2HR (30)<=8.8+0.086W (wherein T2HR (30) is the relaxation time (mus) of the rubbery component as measured at 30 deg.C with pulse NMR, and T2HR (80) is that at 80 deg.C) and 90-5wt.% propylene random copolymer having an intrinsic viscosity [mu]of 0.5-10dl/g and containing 10-80mol% units of an olefin other than propylene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene-based resin composition, and more specifically, it has excellent mechanical properties in a wide elastic modulus range and has a small temperature dependence of the mechanical properties and is molded. The present invention relates to a propylene-based resin composition having no surface tackiness.

[0002]

2. Description of the Related Art Polypropylene resin is known to be a resin having a good balance of rigidity and low temperature impact strength when it is made into a so-called block copolymer. Needed to extremely increase the amount of the copolymerized part. However, although this improves the impact strength, the surface characteristics and heat resistance are unavoidably impaired, and the improvement thereof has been desired. The present inventors have previously disclosed a propylene-based elastomer composition having unprecedented excellent mechanical properties (JP-A-3-168234). However, this product is excellent in mechanical properties, and although some improvement in the above-mentioned problems of surface properties and heat resistance was recognized, it was not always sufficiently satisfactory, and further improvement was necessary.

[0003]

Under the circumstances described above, the present invention has excellent mechanical properties in a wide elastic modulus range, has a small temperature dependence of the mechanical properties, and is molded. The purpose of the present invention is to provide a propylene-based resin composition having no tackiness on the surface of the product.

[0004]

As a result of intensive studies to develop a propylene resin composition having the above-mentioned preferable properties, the present inventors have found that (a) a specific intrinsic viscosity and boiling n-heptane insolubility. Homopolymer of propylene and / or having a content of the components and having a specific relationship between the measured values of the relaxation time of the rubber component measured by pulse NMR at temperatures of 30 ° C. and 80 ° C. and the amount of the boiling n-heptane-insoluble component. Alternatively, a copolymer containing a relatively small amount of other olefin units and (b) a propylene-based random copolymer containing a relatively large amount of other olefin units other than propylene having a specific intrinsic viscosity at a specific ratio. It was found that the purpose can be achieved by the contained propylene resin composition. The present invention is
It was completed based on such knowledge.

That is, according to the present invention, (a) (a) temperature 1
The intrinsic viscosity [η] measured in decalin at 35 ° C is 0.5-
10 deciliters / g, (b) the boiling n-heptane insoluble component amount (W) is 10 to 99% by weight, and (c) the temperature of the relaxation time of the rubber component measured by pulse NMR is 30 ° C.
The relationship between the measured value [T _2H ^R (30): μs] and the measured value at 80 ° C. [T _2H ^R (80): μs] and the boiling n-heptane insoluble component amount (W) is calculated by the formula T _2H ^R (80) ≦ 670−2.2 × W T _2H ^R (80) / T _2H ^R (30) ≦ 8 + 0.086 × W satisfying a homopolymer of propylene and / or 4 mol% or less of other Copolymers containing olefin units 10-95
Propylene-based random copolymerization containing 10% by weight and (b) 10 to 80 mol% of an olefin unit other than propylene having an intrinsic viscosity [η] of 0.5 to 10 deciliter / g measured in decalin at a temperature of 135 ° C. A propylene-based resin composition comprising 90 to 5% by weight of coalescence is provided.

The propylene resin composition of the present invention is
Homopolymer of propylene as component (a) and / or 4
It contains a copolymer containing up to mol% of other olefin units. This propylene homopolymer or copolymer has an intrinsic viscosity [η] of 0.5 when measured in decalin at a temperature of 135 ° C.
It should be in the range of -10 deciliter / g, preferably 1.0-9.0 deciliter / g. If the intrinsic viscosity [η] is less than 0.5 deciliter / g, the mechanical properties are insufficient, and if it exceeds 10 deciliter / g, the moldability deteriorates. Further, it is necessary that the boiling n-heptane insoluble component amount (W) is in the range of 10 to 99% by weight, preferably 20 to 99% by weight. If the amount of this insoluble component deviates from the above range, the object of the present invention cannot be sufficiently achieved. The amount of the insoluble component (W) is a value expressed as a weight fraction of a boiling n-heptane insoluble component after the extraction residue after extraction with boiling n-heptane for 6 hours using a Soxhlet extraction tester.

Further, the propylene homopolymer or copolymer has a relaxation time of a rubber component measured by pulse NMR at a temperature of 30 ° C. [T _2H ^R (30): μs] and 8
The relationship between the measured value at 0 ° C. [T _2H ^R (80): μs] and the amount of the boiling n-heptane insoluble component (W) is calculated by the formula T _2H ^R (80) ≦ 670−2.2 × W T _2H It is necessary to satisfy ^R (80) / T _2H ^R (30) ≦ 8.8 + 0.086 × W. If the above relational expression is not satisfied, the object of the present invention cannot be achieved.

Regarding the method for measuring the relaxation time (T _2H ^R ) of the rubber component by the above-mentioned pulse NMR, a CXP-90NMR apparatus manufactured by Nippon Bruker Co., Ltd. was used, and the observed nucleus was ¹ H at a measurement frequency of 90.1 MHz. The measurement pulse series was measured by the solid echo method. Set the observation pulse width to 2.
The waiting time until the next pulse was given after the observation of 0 μsec and FID (free induction decay) was 5 seconds, and the number of integration was 300 times. The FID was analyzed by the following method.

(1) FID analysis method at a temperature of 30 ° C. FID: M measured by the above measuring method_exp(T)
M calculated by_{ca l}Revised Marcato for (t)
Optimization by the nonlinear least squares method using the method. M_cal(t) = M₀ ^{c + G}exp 〔(t / T_2H ^{C + G})²/ 2] + M₀ ^Rexp (t / T
_2H ^R) In addition, the subscripts R, G, and C each represent rubber-like molecular properties.
An amorphous component, a glassy amorphous component, and a crystalline component are shown. Well
Also, the optimization is M as a variable₀ ^{c + G}, M₀ ^R, T_2H ^{C + G}，
T_2H ^RUsing T as the initial value_2H ^R> 3T_2H ^{C + G}, 1μ
s <T_2H ^{C + G}A value of <15 μs was used.

(2) FID analysis method at a temperature of 80 ° C. M_exp(T) is calculated by the following formula M_calTo (t)
By the nonlinear least squares method using the revised Marquardt method
Optimize. M_cal(t) = M₀ ^cexp 〔(t / T_2H ^C)²/ 2] + M₀ ^Gexp (t / T_2H
^G) + M₀ ^Rexp (t / T_2H ^R) Note that the subscripts are the same as above, and there are
M as a number₀ ^C, M₀ ^R, M₀ ^R, T_2H ^C, T_2H ^G, T
_2H ^RWas used. Further, the propylene resin composition of the present invention
Is an olefin unit other than propylene as the component (b)
10 to 80 mol%, preferably 10 to 70 mol%
It contains a propylene-based random copolymer. This prop
The ren-based random copolymer is in decalin at a temperature of 135 ° C.
Intrinsic viscosity [η] measured at 0.5 to 10 deciliters /
g, preferably 1.0 to 9.0 deciliters / g
It is necessary to This intrinsic viscosity [η] is 0.5 deci
If the amount is less than 1 ton / g, the mechanical properties are insufficient and
If it exceeds Siliter / g, moldability deteriorates.

In the propylene resin composition of the present invention, 10 to 95% by weight, preferably 30 to 95% by weight, of the propylene homopolymer or copolymer as the component (a),
90 to 5 of the propylene random copolymer as the component (b)
It is necessary to contain it in a weight percentage, preferably 70 to 5 wt%. If the content ratio of the component (a) and the component (b) deviates from the above range, the object of the present invention cannot be sufficiently achieved. The propylene-based resin composition of the present invention includes various polymerization methods such as a gas phase multi-step polymerization method and a slurry multi-step polymerization method,
Alternatively, it can be prepared by a blending method. For example, when prepared by a polymerization method, (A) (a) a solid catalyst component composed of magnesium, titanium, a halogen atom and an electron donor, and (b) a solid composed of a crystalline polyolefin which is optionally used. Component, (B) organoaluminum compound, (C) general formula (I)

[0012]

[Chemical 1]

[Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, m is an integer of 1 to 6, and n is 0. ~ (6-m)
Indicates an integer. ] Propylene and other olefins may be polymerized in the presence of a catalyst system composed of an alkoxy group-containing aromatic compound represented by the following formula and (D) an electron-donating compound which is optionally used.

The solid component (A) is composed of the solid catalyst component (a) consisting of magnesium, titanium, a halogen atom and an electron donor, and the crystalline polyolefin (b) which is optionally used. Has been done. The solid catalyst component of the component (a) is magnesium, titanium,
It has a halogen atom and an electron donor as essential components, and can be prepared by contacting a magnesium compound, a titanium compound and an electron donor. In this case, the halogen atom is included as a halide in the magnesium compound and / or the titanium compound.

Examples of the magnesium compound include magnesium dihalides such as magnesium chloride, magnesium oxide, magnesium hydroxide, hydrotalcite, carboxylates of magnesium, alkoxy magnesium such as diethoxy magnesium, allyloxy magnesium, and alkoxy magnesium halides. , Alkyl magnesium such as allyloxy magnesium halide and ethyl butyl magnesium, alkyl magnesium halide, or organomagnesium compound and electron donor,
Examples thereof include reaction products with halosilanes, alkoxysilanes, silanols, aluminum compounds, and the like, and among these, magnesium halides, alkoxymagnesiums, alkylmagnesiums, and alkylmagnesium halides are preferable. These magnesium compounds may be used alone or in combination of two or more.

As the magnesium compound, a reaction product of metallic magnesium, halogen and alcohol can also be used. The metallic magnesium used at this time is not particularly limited, and metallic magnesium having an arbitrary particle size, for example, granular, ribbon-like, powder-like or the like can be used. Further, the surface state of the magnesium metal is not particularly limited, but it is preferable that the surface of the surface is not coated with magnesium oxide. Further, any alcohol can be used, but it has 1 to 6 carbon atoms.
It is preferable to use the lower alcohols mentioned above, and ethanol is particularly preferable because it gives a solid catalyst component that remarkably improves the expression of the catalytic performance. The purity and the water content of the alcohol are not limited, but when an alcohol having a high water content is used, magnesium hydroxide is formed on the surface of metal magnesium. Therefore, it is preferable to use an alcohol having a water content of 1% by weight or less, particularly 2000 ppm or less. Preferably, the lower the water content, the more advantageous.

The type of halogen and / or halogen-containing compound is not limited, and any compound containing a halogen atom in its molecule can be used. in this case,
The type of halogen atom is not particularly limited, but chlorine, bromine or iodine, particularly iodine is preferably used.
Among the halogen-containing compounds, halogen-containing metal compounds are particularly preferable. These states, shapes, particle sizes, etc. are not particularly limited and may be arbitrary, and for example, they can be used in the form of a solution in an alcohol solvent (eg ethanol). The amount of alcohol used is selected in the range of 2 to 100 mol, preferably 5 to 50 mol, per 1 mol of metallic magnesium. If the amount of alcohol is too large, it tends to be difficult to obtain a magnesium compound having a good morphology, and if it is too small, the reaction with metallic magnesium may not be carried out smoothly.

The halogen and / or the halogen-containing compound is usually 0.0001 gram atom or more, preferably 0.0005 gram atom or more, based on 1 mol of magnesium metal.
More preferably, it is used in a proportion of 0.001 gram atom or more. If it is less than 0.0001 gram atom, when the obtained magnesium compound is used without being crushed, the carried amount, activity, stereoregularity, morphology of the produced polymer and the like are lowered, and the crushing treatment becomes indispensable, which is not preferable. Further, by appropriately selecting the amount of halogen used, it is possible to arbitrarily control the particle size of the obtained magnesium compound.

The reaction itself of the magnesium metal, the alcohol, the halogen and / or the halogen-containing compound can be carried out by a known method. For example, metallic magnesium, alcohol, and halogen are usually refluxed under reflux for about 20 to 30 until generation of hydrogen gas is not observed.
This is a method of reacting for a time to obtain a desired magnesium compound. Specifically, for example, when iodine is used as the halogen, a method in which metallic magnesium and solid iodine are put into an alcohol and then heated and refluxed, and an alcohol solution of metallic magnesium and iodine is dropped into the alcohol and then added. Examples thereof include a method of heating and refluxing, a method of dropping an alcohol solution of iodine while heating an alcohol solution containing metallic magnesium, and the like. Both methods are preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas, optionally using an inert organic solvent (for example, saturated hydrocarbon such as n-hexane). Regarding the addition of metal magnesium, alcohol, and halogen, it is not necessary to add all of them to the reaction tank from the beginning, and they may be added separately. A particularly preferable form is a method in which the entire amount of alcohol is charged from the beginning, and metallic magnesium is charged in several times.

In such a case, it is possible to prevent a temporary large amount of hydrogen gas from being generated, which is very desirable from the viewpoint of safety. Also, the reaction tank can be downsized. Furthermore, it becomes possible to prevent the entrainment of alcohol or halogen caused by the temporary large generation of hydrogen gas. The number of times of division may be determined in consideration of the scale of the reaction tank, and usually 5 to 10 times is preferable considering the complexity of the operation. Further, it goes without saying that the reaction itself may be a batch type or a continuous type. Furthermore, as a modified method, a small amount of metallic magnesium is first added to the alcohol that has been entirely added from the beginning, the product produced by the reaction is separated and removed in another tank, and then a small amount of metallic magnesium is added again. It is also possible to repeat. When the magnesium compound thus obtained is used for the next preparation of the solid catalyst component, a dried one may be used, or a magnesium compound that has been filtered and washed with an inert solvent such as heptane may be used. In any case, the obtained magnesium compound can be used in the next step without pulverization or classification operation for adjusting the particle size distribution.

Examples of the titanium compound include tetramethoxy titanium, tetraethoxy titanium and tetra-
n-propoxy titanium, tetraisopropoxy titanium,
Tetra-n-butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium, tetraphenoxytitanium and other tetraalkoxytitaniums, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and other tetrahalogenated titanium, and methoxytitanium trichloride. , Ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide and other halogenated alkoxytitanium, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride , Dialkoxytitanium dialkoxytitanium such as diethoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium Rorido, tripropoxy titanium chloride, but such monohalogenated trialkoxy titanium and tri -n- butoxy titanium chloride and the like, high halogen-containing titanium compound Among these, particularly titanium tetrachloride is preferred. These titanium compounds may be used alone or in combination of two or more.

Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and these halogen atoms are usually used as a halide contained in a magnesium compound and / or a titanium compound. . Further, as the electron donor, (D) will be used later.
What was illustrated as an electron donative compound of a component can be used. The (a) solid catalyst component can be prepared by a known method (JP-A-53-43094, JP-A-55-13).
5102, JP-A-55-135103, JP-A-56-18606, JP-A-56-16620.
No. 5, JP-A-57-63309, JP-A-57.
-190004, JP-A-57-300407, JP-A-58-47003).

The composition of the solid catalyst component (a) thus prepared usually has a magnesium / titanium atomic ratio of 2 to
100, the halogen / titanium atomic ratio is in the range of 5 to 100, and the electron donor / titanium molar ratio is in the range of 0.1 to 10. Also,
Examples of the crystalline polyolefin (B) that is used as necessary in the preparation of the solid component (A) include:
Polyethylene, polypropylene, polybutene, poly 4-
A crystalline polyolefin obtained from an α-olefin having 2 to 10 carbon atoms such as methyl-1-pentene can be mentioned. This crystalline polyolefin is (1) a method of prepolymerizing an olefin in the presence of (1) a combination of the solid catalyst component, an organoaluminum compound and an electron-donating compound used as necessary (preliminary polymerization method). ), (2) crystalline powder such as crystalline polyethylene or polypropylene having a uniform particle size, (a) the solid catalyst component, an organoaluminum compound optionally used and an electron donating compound (melting point 100 ° C. or higher) Can be obtained by using a method of dispersing and (dispersion method), (3) a method of combining the method of (1) and the method of (2), and the like.

In the prepolymerization method (1), the aluminum / titanium atomic ratio is usually selected in the range of 0.1 to 100, preferably 0.5 to 5, and the electron donor compound / titanium molar ratio is set. It is selected in the range of 0 to 50, preferably 0.1 to 2. Regarding the ratio of (a) solid catalyst component and (b) crystalline polyolefin in (A) solid component,
The weight ratio of component (b) to component (a) is usually 0.33.
To 200, preferably 0.1 to 50.

Next, as the organoaluminum compound used as the component (B), general formula (II) AlR ³ _p X _3-p (II) [wherein, R ³ has 3 to 20 carbon atoms] An alkyl group or an aryl group having 6 to 20 carbon atoms, X is a halogen atom, and p is 1 to 3
Indicates the number of. ] The compound represented by these can be mentioned. For example, triisopropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trioctyl aluminum, diethyl aluminum monochloride, diisopropyl aluminum monochloride,
Dialkyl aluminum monohalides such as diisobutyl aluminum monochloride and dioctyl aluminum monochloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, and the like can be preferably used. These aluminum compounds may be used alone or in combination of two or more.

In the catalyst system of the present invention, as the component (C), the general formula (I) is used.

[0027]

[Chemical 2]

[Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, m is an integer of 1 to 6, and n is 0. ~ (6-m)
Indicates an integer. ] An alkoxy group-containing aromatic compound represented by the following is used.

Specific examples of the alkoxy group-containing aromatic compound include m-methoxytoluene; o-methoxyphenol; m-methoxyphenol; 2-methoxy-4-.
Methylphenol; vinylanisole; p- (1-propenyl) anisole; p-allylanisole; 1,3-
Bis (p-methoxyphenyl) -1-pentene; 5-allyl-2-methoxyphenol; 4-hydroxy-3-
Methoxybenzyl alcohol; methoxybenzyl alcohol; nitroanisole; monoalkoxy compounds such as nitrophenetole; o-dimethoxybenzene; m-dimethoxybenzene; p-dimethoxybenzene; 3,4-
Dimethoxytoluene; 2,6-dimethoxyphenol;
Dialkoxy compounds such as 1-allyl-3,4-dimethoxybenzene, 1,3,5-trimethoxybenzene; 5
-Allyl-1,2,3-trimethoxybenzene; 5-allyl-1,2,4-trimethoxybenzene; 1,2,3
-Trimethoxy-5- (1-propenyl) benzene;
1,2,4-trimethoxy-5- (1-propenyl) benzene; 1,2,3-trimethoxybenzene; 1,2,
Examples thereof include trialkoxy compounds such as 4-trimethoxybenzene, and among these, dialkoxy compounds and trialkoxy compounds are preferable. These alkoxy group-containing aromatic compounds may be used alone,
You may use it in combination of 2 or more type.

Further, an electron donating compound is used as the component (D) in the catalyst, if necessary. This electron-donating compound is a compound containing oxygen, nitrogen, phosphorus, sulfur, silicon and the like, and basically, it is considered that it has an ability to improve regularity in the polymerization of propylene.
Examples of such electron-donating compounds include organosilicon compounds, esters, thioesters, amines,
Ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides,
Examples thereof include aldehydes, organic acids and azo compounds.

For example, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane. , Phenyltriethoxysilane, benzyltrimethoxysilane and other organosilicon compounds, monomethylphthalate, monoethylphthalate, monopropylphthalate, monobutylphthalate,
Monoisobutyl phthalate, monoamyl phthalate, monoisoamyl phthalate, monomethyl terephthalate,
Monoethyl terephthalate, monopropyl terephthalate, monobutyl terephthalate, monoisobutyl terephthalate, dimethyl phthalate, diethyl phthalate,
Dipropylphthalate, dibutylphthalate, diisobutylphthalate, diamylphthalate, diisoamylphthalate, methylethylphthalate, methylisobutylphthalate, methylpropylphthalate, ethylbutylphthalate, ethylisobutylphthalate, ethylpropylphthalate, propylisobutylphthalate, dimethylterephthalate, diethyl Terephthalate, dipropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl isobutyl terephthalate, methyl propyl terephthalate, ethyl butyl terephthalate, ethyl isobutyl terephthalate, ethyl propyl terephthalate, propyl isobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate, diproth Aromatic dicarboxylic acid ester such as ruisophthalate, diisobutylisophthalate, methylethylisophthalate, methylisobutylisophthalate, methylpropylisophthalate, ethylbutylisophthalate, ethylisobutylisophthalate, ethylpropylisophthalate, propylisobutylisophthalate, Methyl formate, ethyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate,
Ethyl butyrate, Ethyl valerate, Methyl chloroacetate, Ethyl dichloroacetate, Methyl methacrylate, Ethyl crotonate, Ethyl bivalate, Dimethyl maleate, Ethyl cyclohexanecarboxylate, Methyl benzoate, Ethyl benzoate, Propyl benzoate, Benzoic acid Butyl, octyl benzoate, cyclohexyl benzoate, phenyl benzoate,
Benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,
Monoesters such as ethyl p-butoxybenzoate, ethyl o-chlorobenzoate and ethyl naphthoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide,
Esters such as ethylene carbonate, organic acids such as benzoic acid and p-oxybenzoic acid, acid anhydrides such as succinic anhydride, benzoic anhydride and p-toluic anhydride, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone , Ketones such as benzoquinone, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, tolualdehyde, benzaldedo, naphthylaldehyde, acetyl chloride, acetylbromide, propionyl chloride, butyryl chloride, isobutyryl chloride, 2-methylpropionyl chloride. , Valeryl chloride, isovaleryl chloride, hexanoyl chloride, methylhexanoyl chloride, 2-ethylhexanoyl chloride, octanoyl chloride, decanoyl chloride Lido, undecanoyl chloride, hexadecanoyl chloride, octadecanoyl chloride, henzyl carbonyl chloride, dichlorohexanecarbonyl chloride, malonyl dichloride, succinyl dichloride, pentanedioleyl dichloride, hexanedioleyl dichloride, diclohexanedicarbonyl dichloride, benzoyl Acid halides such as chloride, benzoyl bromide, methylbenzoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, benzene-1,2,4-tricarbonyltrichloride, methyl ether, ethyl ether, isopropyl ether , N-butyl ether, isopropyl methyl ether, isopropyl ethyl ether, t-butyl ethyl ether, t-butyl-n-p Pyrether, t-butyl-n-butyl ether, t-amyl methyl ether, t-amyl ethyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether and other ethers, acetic acid amide, benzoic acid amide, toluic acid amide Acid amides such as, tributylamine, N, N′-dimethylpiperazine, tribenzylamine, aniline, pyridine, pyrroline, tetramethylethylenediamine and other amines, acetonitrile, benzonitrile, tolunitrile and other nitriles, 2,2 ′ -Azo compounds such as azobis (2-methylpropane), 2,2'-azobis (2-ethylpropane), 2,2'-azobis (2-methylpentane) having a sterically hindering substituent bonded to the azo bond And so on It is.

Of these, organosilicon compounds, esters, ketones, ethers, thioethers, acid anhydrides, and acid halides are preferable, and particularly, organosilicon compounds such as diphenyldimethoxysilane and phenyltriethoxysilane, and diphenyldiethoxysilane. Aromatic dicarboxylic acid diesters such as -n-butyl phthalate and diisobutyl phthalate, benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid,
Preference is given to alkyl esters of aromatic monocarboxylic acids such as toluic acid. These electron donating compounds may be used alone or in combination of two or more. Regarding the amount of each component of the catalyst system used, the solid component (A) is used in an amount of usually 0.0005 to 1 mol per 1 liter of reaction volume in terms of titanium atom. The organoaluminum compound (B) is used in an amount such that the aluminum / titanium atom ratio is usually 1 to 3000, preferably 40 to 800. If the amount deviates from the above range, the catalytic activity is insufficient. May be. Further, the (C) alkoxy group-containing aromatic compound is used in such a proportion that the molar ratio to the titanium atom in the (A) solid component is usually 0.01 to 500, preferably 1 to 300. If it is less than 0.01, the physical properties of the polymer produced may be deteriorated, and if it exceeds 500, the catalytic activity may be insufficient.

The propylene-based resin composition of the present invention can be obtained by multistage polymerization in the presence of the above-mentioned catalyst system. The polymerization order and the number of polymerization stages in the multi-stage polymerization can be arbitrarily selected. For example, the first polymerization (first-stage polymerization) can be a homopolymerization of propylene, and the ethylene-propylene-copolymerization or the ethylene-propylene-polyene-copolymerization can be performed after the second stage. Examples of the polyene that can be used include dicyclopentadiene and tricyclopentadiene. The polymerization method is not particularly limited, and slurry polymerization, gas phase polymerization,
Bulk polymerization, solution polymerization, suspension polymerization, etc. are used. When conducting the polymerization by gas phase polymerization, the polymerization pressure is usually 10 to 45 kg / c for the homopolymerization stage of propylene.
m ² , preferably 20 to 30 kg / cm ² , and the polymerization temperature is appropriately selected in the range of usually 40 to 90 ° C, preferably 60 to 75 ° C. Regarding the ethylene-propylene copolymerization stage and the ethylene-propylene-polyene copolymerization stage, the polymerization pressure is usually 5 to 30 kg / cm ² , preferably 10 to 20 kg / cm ² , and the polymerization temperature is usually 20 to 90.
C, preferably selected in the range of 40 to 60C. At any stage, the molecular weight of the polymer can be adjusted by known means, for example, adjusting the hydrogen concentration in the polymerization vessel. It can also be adjusted by melt-kneading in the presence of an organic peroxide. The polymerization time is appropriately selected from about 5 minutes to 10 hours.

In the polymerization, even if the components constituting the catalyst system, that is, the components (A) to (D) are mixed in a predetermined ratio and brought into contact with each other, the olefin is immediately introduced to initiate the polymerization. After the contact, the olefin may be introduced after aging for about 0.2 to 3 hours. Furthermore, this catalyst component can be supplied by suspending it in an inert solvent or olefin. Post-treatment after polymerization can be carried out by a conventional method. That is, in the gas phase polymerization method, after the polymerization, a nitrogen stream or the like may be passed through the polymer powder discharged from the polymerization vessel in order to remove the olefin and the like contained therein. If desired, pelletizing may be carried out by an extruder, and in this case, a small amount of water, alcohol or the like may be added in order to completely deactivate the catalyst. Further, in the bulk polymerization method, after the polymerization, the monomer may be completely separated from the polymer discharged from the polymerization vessel, and then pelletized. The propylene-based resin composition of the present invention is prepared by blending a propylene homopolymer and an ethylene-propylene copolymer and / or a propylene-polyene copolymer by a known method (for example, dry blending or kneading). It can also be prepared.

[0035]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 (1) Preparation of magnesium compound A glass reactor equipped with a stirrer (internal volume of about 6 liters) was sufficiently replaced with nitrogen gas, and about 2430 g of ethanol, 16 g of iodine and 160 g of magnesium metal were charged. While stirring, the mixture was reacted under heating under reflux conditions until no hydrogen gas was generated from the system, and a solid reaction product was obtained. The reaction mixture containing this solid product was dried under reduced pressure to obtain a magnesium compound. (2) Preparation of solid catalyst component (A) In a glass three-necked flask (internal volume of 500 ml) sufficiently replaced with nitrogen gas, 16 g of the magnesium compound (not crushed), 80 ml of purified heptane, and silicon tetrachloride. 2.4 ml and 2.3 ml diethyl phthalate were added. After maintaining the system at 90 ° C. and adding 77 ml of titanium tetrachloride while stirring and reacting at 110 ° C. for 2 hours, solid components were separated and washed with purified heptane at 80 ° C. Further, 122 ml of titanium tetrachloride was added, the mixture was reacted at 110 ° C. for 2 hours, and then thoroughly washed with purified heptane to obtain a solid catalyst component (A).

(3) Gas phase polymerization In a pressure-resistant stainless steel autoclave of 5 liters, polypropylene powder 20 g, triisobutylaluminum (TIBA) 2.5 mmol, 1-allyl-3,4-dimethoxybenzene (ADMB) 0.125 mmol. , 20 ml of a heptane solution containing 0 mmol of diphenyldimethoxysilane (DPDMS) and 0.05 mmol of the above solid catalyst component (A) in terms of titanium atom was added, and the system was evacuated for 5 minutes, and then the total pressure was 28 kg / cm ^2. Gas phase polymerization was carried out for 1.7 hours while supplying propylene gas until G was reached. Next, the unreacted gas in the autoclave was evacuated, and a small amount of the produced powder for analysis was sampled. Then, hydrogen gas 0.5 kg / cm ² G, ethylene - propylene mixed gas (molar ratio 1/1) 10kg / cm ² G
To 50 ° C. for 1.0 hour to carry out gas phase polymerization. The composition and physical properties of the obtained polymer are shown in Table 1.

Example 2 Using the same catalyst as in Example 1, TIBA during gas phase polymerization,
The amount of ADMB and DPDMS was 5.0 mmol,
After homopolymerization of propylene in the same manner as in Example 1 with the amounts of 0.125 and 0.2 mmol, the gas composition and the polymerization time in the copolymerization were adjusted so that the compositions shown in Table 1 were obtained. The results are shown in Table 1.

Example 3 Using the same catalyst as in Example 1, TIBA during gas phase polymerization,
The amount of ADMB and DPDMS was 5.0 mmol,
Propylene homopolymerization was carried out in the same manner as in Example 1 with the amounts of 0.125 mmol and 0.4 mmol, and then the gas composition and the polymerization time in the copolymerization were adjusted so that the compositions shown in Table 1 were obtained. The results are shown in Table 1.

Example 4 Using the same catalyst as in Example 1, TIBA during gas phase polymerization,
The amount of ADMB and DPDMS was 5.0 mmol,
Propylene homopolymerization was carried out in the same manner as in Example 1 with the amounts of 0.125 mmol and 0.5 mmol, and then the gas composition and the polymerization time in the copolymerization were adjusted so that the compositions shown in Table 1 were obtained. The results are shown in Table 1.

Example 5 The same procedure as in Example 2 was carried out until propylene homopolymerization.
Regarding the copolymerization, the gas composition and the polymerization time were adjusted so that the composition shown in Table 1 was obtained. The results are shown in Table 1.

Examples 6 to 8 After homopolymerization of propylene in the same manner as in Example 2, the gas composition and the polymerization time in the copolymerization were adjusted so that the compositions shown in Table 1 were obtained. The results are shown in Table 1. Comparative Example 1 (1) Preparation of solid catalyst component 20 ml of purified heptane was added to a glass three-necked flask having an inner volume of 500 ml that had been sufficiently replaced with nitrogen.
4 g of Mg (OC ₂ H ₅ ) ₂ and di-n-butyl phthalate 1.
Add 2g and keep the system temperature at 90 ° C.
After adding 4 ml of Cl ₄ , add more TiCl
_An additional 111 ml of ₄ was added, the temperature was raised to 110 ° C, the reaction was performed for 2 hours, and then purified heptane 1 at 80 ° C
Washed with 00 ml. Next, 115 ml of TiCl ₄ was added to the obtained solid phase portion, and the mixture was further reacted at 110 ° C. for 2 hours. After the reaction was completed, the product was washed several times with 100 ml of purified heptane to obtain a solid catalyst component.

(2) Preparation of solid component In a pressure-resistant three-necked glass flask with an internal volume of 2.5 liters, which had been sufficiently replaced with nitrogen, 1.7 liters of purified heptane and Al
(C ₂ H ₅ ) ₃ 0.07 mol, diphenyldimethoxysilane (DPDMS) 0.05 mmol and 120 g of the solid catalyst component obtained in the above (1) were added, and the system was kept at 30 ° C. and stirred. While supplying propylene continuously, the internal pressure was maintained at 0.5 kg / cm ² G. After continuing this reaction for 1 hour, it was washed 5 times with 1 liter of purified heptane,
A solid component was prepared.

(3) Gas phase polymerization In a pressure resistant autoclave made of stainless steel of 5 liters, 20 g of polypropylene powder, 3 mmol of Al (C ₂ H ₅ ) ₃ , 0.15 mmol of ADMB, 0.23 mmol of DPDMS and the solid of (2) above. 20 ml of a heptane solution containing 100 mg of the component (0.06 mmol in terms of titanium atom) was added, the system was evacuated for 5 minutes, and then propylene gas was supplied until the total pressure reached 28 kg / cm ² G. Gas phase polymerization was carried out at 70 ° C. for 1.7 hours. Then
After exhausting unreacted gas, add 0.5 kg / cm of hydrogen gas
² G, ethylene-propylene mixed gas (molar ratio 1/3)
Was supplied to 10 kg / cm ² G and vapor phase polymerization was carried out at 50 ° C. for 1.2 hours. The results are shown in Table 1.

Comparative Examples 2 to 4 In the gas phase first stage polymerization (propylene homopolymerization),
The same procedure as in Comparative Example 1 was carried out except that the boiling n-heptane-insoluble component amount W (stereoregularity) was adjusted by the amounts of ADMB and DPDMS, and the composition was adjusted by the gas composition and the polymerization time in the copolymerization. The results are shown in Table 1.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

The propylene resin composition of the present invention has high heat resistance and excellent mechanical properties in a wide elastic modulus range,
In addition, it has excellent characteristics such as low temperature dependence of its mechanical properties and no stickiness on the surface of the molded product. Examples of the propylene resin composition include side moldings, over fenders, mudguards, soft bumpers, handles, shift knobs, armrests, console boxes,
It is preferably used as an automobile part such as a seat, and also as a material for civil engineering and construction materials, films and sheets.

Claims (1)

[Claims] (A) (a) The intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C. is 0.5 to 10 deciliter /
(b) boiling n-heptane insoluble component amount (W) is 10
˜99% by weight, and (c) measured value of the relaxation time of the rubber component measured by pulse NMR at a temperature of 30 ° C. [T
_2H ^R (30): μs] and measured value at 80 ° C [T _2H ^R (8
0): μs] and the amount of insoluble component of boiling n-heptane (W)
A propylene homopolymer satisfying the formula T _2H ^R (80) ≦ 670−2.2 × W T _2H ^R (80) / T _2H ^R (30) ≦ 8.8 + 0.086 × W and / Or copolymers 10 to 95 containing 4 mol% or less of other olefin units
Propylene-based random copolymerization containing 10% by weight and (b) 10 to 80 mol% of olefin units other than propylene having an intrinsic viscosity [η] of 0.5 to 10 deciliter / g measured in decalin at a temperature of 135 ° C. A propylene-based resin composition composed of 90 to 5% by weight of the combined product.