JPH06263934A - Soft polypropylene resin - Google Patents

Abstract

PURPOSE:To obtain the subject resin having excellent heat-resistance, scratch resistance, low-temperature impact resistance, etc., producible at a low cost and useful for automobile parts, etc., by compounding two kinds of PP polymers having specific properties and obtained by a vapor-phase/slurry single stage polymerization. CONSTITUTION:This resin composition is composed of (A) 10-90wt.% of a PP having an intrinsic viscosity of >=1.2dL/g and soluble in boiling heptane and (B) 90-10wt.% of a PP having an intrinsic viscosity of 0.5-9.0dL/g and insoluble in boiling heptane. These PP polymers are produced by a vapor-phase single stage polymerization or a slurry single stage polymerization. The pentad fraction of the composition determined by <13>C nuclear magnetic resonance absorption is preferably >=20% in terms of rrrr/l-mmmm and the melt peak temperature and melt enthalpy determined by differential scanning calorimetry are >=150 deg.C and <=100J/g, respectively.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel soft polypropylene resin. More specifically, the present invention is obtained by a gas-phase one-step polymerization method or a slurry one-step polymerization method, and has mechanical properties comparable to those of a partially cross-linked olefinic thermoplastic elastomer (TPO) without a cross-linking treatment. The present invention relates to a soft polypropylene resin which has a favorable cost and is suitable as a thermoplastic elastomer material.

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomers have been used as new materials for filling the gap between rubber and plastic, and as energy-saving and resource-saving type elastomers, especially as substitutes for vulcanized rubber, such as automobile parts such as bumpers and side moldings. Firstly, it is widely used for industrial machinery parts, electrical parts, civil engineering / construction material sheets, and waterproofing materials.

As such a thermoplastic elastomer, a partially crosslinked olefinic thermoplastic elastomer (TPO) is widely used because it has excellent mechanical properties as a thermoplastic elastomer. However, polypropylene and ethylene-propylene-diene rubber (EPD) are commonly used to produce this TPO.
M) is kneaded in the presence of a peroxide, the operation is complicated, and it is necessary to use a peroxide.
POs are inevitably expensive.

Therefore, by preparing a polymer having mechanical properties similar to those of TPO at the polymerization stage,
Various attempts have been made to reduce the cost. For example, a propylene-hexene copolymer (Japanese Unexamined Patent Publication No.
9-53983, Japanese Patent Publication No. 62-19444), and elastic polypropylene (Japanese Patent Laid-Open No. 61-179247).
No. gazette) is proposed. However, all of these polymers have the drawback of insufficient low temperature properties.

In order to improve the low temperature characteristics of polypropylene, a two-stage propylene / ethylene-propylene polymerization method is well known (see, for example, JP-A-57-508).
No. 04), this method makes it difficult to produce a polymer having both flexibility and practical tensile strength. On the other hand, polypropylene is industrially produced by using a Ziegler type catalyst, but in this case, mainly crystalline isotactic polypropylene is produced, and about 1
0-15% atactic polypropylene is by-produced.
This atactic polypropylene has a number average molecular weight (M
n) was as low as about 10,000, and its practical value was poor.

By the way, the present inventors have previously proposed a catalyst comprising a combination of a solid catalyst component containing magnesium, titanium, a halogen atom and an electron donor as essential components, an organoaluminum compound and an aromatic compound containing an alkoxy group. It was found that a high molecular weight atactic polypropylene can be easily obtained by polymerizing propylene using a system (JP-A-63-243106). The atactic polypropylene obtained by this method is soluble in boiling heptane and has a molecular weight of usually 25,000.
It has a feature that it is as high as about 0 to 100,000 and the molecular weight distribution is relatively narrow. Although this atactic polypropylene has properties as a rubber-like elastic body and excellent melting properties, it has a problem that it has insufficient mechanical strength and cannot be used alone as a molding material.

[0007]

Under the circumstances, the present invention has good mechanical properties as a thermoplastic elastomer and is advantageous in terms of cost. For example, a bumper in the automobile field. The purpose of the present invention is to provide a thermoplastic elastomer material suitable for use as a building material sheet, a water blocking material, and the like in the field of civil engineering and construction.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have obtained a gas phase one-step polymerization method or a slurry one-step polymerization method, and have a specific intrinsic viscosity. A soft polypropylene resin containing an atactic polypropylene component (boiling heptane-soluble polypropylene component) having a certain ratio and an isotactic polypropylene component (boiling heptane-insoluble polypropylene component) having a specific intrinsic viscosity in a predetermined ratio is suitable for the purpose. It has been found that this can be done, and the present invention has been completed based on this finding.

That is, the present invention is a soft polypropylene resin obtained by a gas-phase one-step polymerization method or a slurry one-step polymerization method, wherein (a) a boiling heptane-soluble polypropylene having an intrinsic viscosity [η] of 1.2 dl / g or more. 10 to 90% by weight, and (b) intrinsic viscosity [η] is 0.5 to 9.0 dl / g
Boiling heptane insoluble polypropylene 90 to 10% by weight
And a soft polypropylene resin composed of

The soft polypropylene resin of the present invention has an intrinsic viscosity [η] of 1.2 dl / g or more, preferably 1.5 d.
1 / g or more of a boiling heptane-soluble polypropylene component and an intrinsic viscosity [η] of 0.5 to 9.0 dl / g, preferably 1.0 to 6.0 dl / g of a boiling heptane-insoluble polypropylene component, and The contents of the boiling heptane-soluble polypropylene component and the boiling heptane-insoluble polypropylene component are 10 to 90% by weight and 90%, respectively.
-10% by weight, preferably 25-70% by weight and 75-
It must be in the range of 30% by weight.

If the intrinsic viscosity [η] of the boiling heptane-soluble polypropylene component is less than 1.2 dl / g, the stress at break is low and the rubber elasticity may be impaired. If the content of the boiling heptane-soluble polypropylene is less than 10% by weight, flexibility may be impaired, and if it exceeds 90% by weight, sufficient mechanical strength may not be obtained. On the other hand, when the intrinsic viscosity [η] of the boiling heptane-insoluble polypropylene component is less than 0.5 dl / g, the impact resistance is extremely poor, and when it exceeds 9.0 dl / g, molding tends to be difficult. The intrinsic viscosity [η] is a value measured in a decalin solution at a temperature of 135 ° C.

The soft polypropylene resin of the present invention comprises ¹³ C
-In the pentad fraction by nuclear magnetic resonance absorption method ( ^13C -NMR), rrrr / 1-mmmm is 20% or more, and the melting peak temperature (Tm) and melting determined by the differential scanning calorimetry (DSC) Enthalpy (ΔH)
Are particularly preferably 150 ° C. or higher and 100 J / g or lower, respectively. The rrrr / 1-mmmm is 2
If it is less than 0%, the low temperature impact resistance is poor and the Tm is 150 ° C.
When it is less than 1, sufficient heat resistance cannot be obtained, and the ΔH is 10
If it is less than 0 J / g, the flexibility may be impaired and sufficient physical properties as a thermoplastic elastomer may not be obtained. Furthermore, in the soft polypropylene resin of the present invention, a domain structure is usually observed by observation with a transmission electron microscope.

The soft polypropylene resin of the present invention as described above can be produced by a gas phase one-step polymerization method or a slurry one-step polymerization method. In the gas phase one-stage polymerization method, for example, (a) a solid catalyst component containing magnesium, titanium, a halogen atom and an electron donor as essential components,
(B) A solid component prepared by prepolymerizing an olefin in the presence of a combination of an organoaluminum compound and (d) an electron donor which is optionally used, or crystalline polypropylene or polyethylene having a uniform particle size. A solid component obtained by dispersing (a) the solid catalyst component, (b) an organoaluminum compound and (d) an electron donor (melting point of 100 ° C. or more) optionally used in the crystalline polyolefin powder of The solid component obtained by combining these methods is used as the component (I), and (II) an organoaluminum compound, (III) an alkoxy group-containing aromatic compound, and (IV) an electron donor used as desired. The desired soft polypropylene resin is obtained by polymerizing propylene in the presence of a combined catalyst.

When the method of prepolymerizing an olefin is used in the preparation of the solid component (I), examples of the olefin include ethylene, propylene, butene-1,
An α-olefin having 2 to 10 carbon atoms such as 4-methylpentene-1 is used, and usually 30 to 80 ° C., preferably 55.
Prepolymerization is carried out at a temperature in the range of to 70 ° C to form a crystalline polyolefin having a melting point of 100 ° C or higher. At this time, the aluminum / titanium atomic ratio of the catalyst system is usually selected in the range of 0.1 to 100, preferably 0.5 to 5, and the electron donor / titanium molar ratio is 0 to 50.
It is preferably selected in the range of 0.1 to 2.

The ratio of the crystalline polyolefin to the solid catalyst component (a) in the solid component (I) is 1: 3 by weight.
0 to 200: 1, preferably 1:10 to 50:
It is preferably in the range of 1. Regarding the amount of each catalyst component used in this gas-phase one-stage polymerization method, the solid component (I) is usually used in an amount of 0.0005 to 1 mol per 1 liter of reaction volume in terms of Ti atoms. Also,
(III) Alkoxy group-containing aromatic compound / (I) Ti molar ratio in solid component is 0.01 to 500, preferably 1 to
300, the Al / Ti atomic ratio is 1 to 3000, preferably 40 to 800, and the (III) alkoxy group-containing aromatic compound / (IV) electron donor molar ratio is 0.01 to 100,
Each component is preferably used so as to be 0.2 to 100. (III) Alkoxy group-containing aromatic compound /
If the molar ratio of Ti in the solid component (I) is less than 0.01, it is difficult to obtain a polymer having the desired physical properties, and if it exceeds 500, the catalytic activity tends to decrease, and Al / T
If the i atomic ratio deviates from the above range, the catalytic activity tends to be insufficient.

Regarding the polymerization conditions in this gas phase one-stage polymerization method, the polymerization temperature is usually 40 to 90 ° C., preferably 60 to 75 ° C., and the polymerization pressure is usually 10 to 4
5 kg / cm ² · G, preferably 20-30 kg / cm
It is selected within the range of ² · G, and the polymerization time of about 5 minutes to 10 hours is sufficient. At this time, the molecular weight control of the polymer is
It can be carried out by a known method, for example, by adjusting the hydrogen concentration.

On the other hand, in the slurry one-stage polymerization method, 2
A variety of catalyst systems can be used to produce soft polypropylene polymers. The first catalyst system is usually (a) a solid catalyst component containing magnesium, titanium, a halogen atom and an electron donor as essential components, (b) an organoaluminum compound, and (c) an alkoxy group-containing aromatic compound. And can be prepared by bringing them into contact with each other using a hydrocarbon solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as hexane and heptane, benzene,
Examples thereof include halogenated hydrocarbons such as mono- or polyhalides of saturated or unsaturated aliphatic, aromatic or alicyclic hydrocarbons having 1 to 12 carbon atoms such as toluene, and these may be used alone. However, two or more kinds may be used in combination.

Regarding the amount of each component used in this catalyst system, the solid catalyst component (a) is usually used in an amount of 0.0005 to 1 mol per liter of reaction volume in terms of Ti atom. (C) The molar ratio of Ti in the alkoxy group-containing aromatic compound / (A) solid catalyst component is 0.0
Each component is used in a ratio of 1 to 500, preferably 1 to 300, and an Al / Ti atomic ratio of 1 to 3000, preferably 40 to 800. When the molar ratio of Ti in the (c) alkoxy group-containing aromatic compound / (a) solid catalyst component is less than 0.01, it is difficult to obtain a polymer having desired physical properties, while when it exceeds 500, the catalytic activity is lowered. There is a tendency to do. Further, when the Al / Ti atomic ratio deviates from the above range, the catalytic activity tends to be insufficient.

On the other hand, the second catalyst system usually has the above-mentioned (a)
The solid catalyst component and (c) an alkoxy group-containing aromatic compound are reacted in the presence or absence of (b) an organoaluminum compound to obtain (I) a solid component, and this solid component and (II) an organoaluminum compound It can be prepared by contacting with. When the solid component (I) is prepared in the presence of (b) the organoaluminum compound,
The concentration of the organoaluminum compound is usually 0.0
It is used in an amount of 5 to 100 mmol / liter, preferably 1 to 10 mmol / liter. If this concentration is less than 0.05 mmol / liter, the effect of the presence of the organoaluminum compound is not sufficiently exhibited, and 1
When it exceeds 00 mmol / liter, (a) the reduction of titanium in the solid catalyst component proceeds, and the catalytic activity tends to decrease.

On the other hand, when the solid component (I) is prepared in the absence of the (b) organoaluminum compound,
(C) Alkoxy group-containing aromatic compound / (a) Ti molar ratio in the solid catalyst component is 0.1 to 200, preferably 1 to
So that the concentration of the (c) alkoxy group-containing aromatic compound is 0.01 to 10 mmol / liter, preferably 0.1 to 2 mmol / liter.
Each component is used. If the concentration of the alkoxy group-containing aromatic compound is less than 0.01 mmol / liter, the volumetric efficiency is low and it is not practical, and if it exceeds 10 mmol / liter, overreaction is apt to occur and the catalytic activity tends to decrease. .

Regarding the reaction conditions for preparing the solid component (I), the reaction temperature is usually selected in the range of 0 to 150 ° C, preferably 10 to 50 ° C. If this temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and if it exceeds 150 ° C., a side reaction occurs and the catalytic activity tends to decrease.
Also, the reaction time depends on the temperature, but is usually 1
~ 200 minutes, preferably about 10-60 minutes.

Regarding the amounts of the solid component (I) and the organoaluminum compound (II) used in the second catalyst system, the solid component (I) is usually 0 in terms of Ti atom per 1 liter of reaction volume. 0.0005 to 1 mol, and the Al / Ti atomic ratio is usually 1 to 30.
Each component is used in a ratio of 00, preferably 40 to 800. If the Al / Ti atomic ratio deviates from the above range, the catalytic activity tends to be insufficient.

When the soft polypropylene resin of the present invention is produced by the slurry one-step polymerization method using the first catalyst system or the second catalyst system thus prepared,
The reaction temperature is generally 0 to 200 ° C., preferably 60 to 10
It is selected in the range of 0 ° C, and the reaction pressure is usually 1 to 50 kg.
/ Cm ² · G is selected. A polymerization time of about 5 minutes to 10 hours is sufficient. At this time, the molecular weight of the polymer can be adjusted by a known method such as adjusting the hydrogen concentration.

Such a gas-phase one-step polymerization method or slurry 1
10 to 90% by weight of boiling heptane-soluble polypropylene having an intrinsic viscosity [η] of 1.2 dl / g or more by a step polymerization method.
And (b) 90 to 10% by weight of boiling heptane-insoluble polypropylene having an intrinsic viscosity [η] of 0.5 to 9.0 dl / g, the soft polypropylene resin of the present invention can be obtained.

(A) A method for preparing a solid catalyst component used as a catalyst in the gas phase one-step polymerization method and a slurry one-step polymerization method, a raw material magnesium compound or titanium compound used for the preparation, and a catalyst Variously used organoaluminum compounds, alkoxy group-containing aromatic compounds,
The following may be used as the electron donor.

First, the solid catalyst component (a) used as a catalyst in the gas-phase one-step polymerization method and the slurry one-step polymerization method contains magnesium, titanium, a halogen atom and an electron donor as essential components, and is usually , A magnesium compound, a halogen-containing titanium compound, and an electron donor.

Examples of the magnesium compound used in the preparation of the solid catalyst component (a) include magnesium dihalides such as magnesium dichloride, magnesium oxide, magnesium hydroxide, hydrotalcite, carboxylates of magnesium, diethoxymagnesium, etc. Alkoxy magnesium, allyloxy magnesium,
Alkoxy magnesium halides, allyloxy magnesium halides, alkyl magnesium such as ethylbutyl magnesium, alkyl magnesium halides, or organic magnesium compounds and electron donors, halosilanes,
Examples thereof include alkoxysilane, silanol, and a reaction product with an aluminum compound. Among these, magnesium halide, alkoxymagnesium,
Alkyl magnesium and alkyl magnesium halide are preferable. In addition, these magnesium compounds are 1
The seeds may be used, or two or more kinds may be used in combination.

Examples of the titanium compound used in the preparation of the solid catalyst component (a) include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, and tetra-n-butoxy titanium. Tetraalkoxy titanium such as isoptoxy titanium, tetracyclohexyloxy titanium, tetraphenoxy titanium, titanium tetrachloride, titanium tetrabromide,
Titanium tetraiodide such as titanium tetraiodide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, trihalogenated alkoxytitanium such as ethoxytitanium tribromide, dimethoxytitanium dichloride, dititanium Ethoxytitanium dichloride, dipropoxytitanium dichloride, di-n
-Dihalogenated dialkoxytitanium such as propoxytitanium dichloride and diethoxytitanium dibromide, monohalogenated trialkoxytitanium such as trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride and tri-n-butoxytitanium chloride. Can be mentioned,
Among these, high halogen content titanium compounds, particularly titanium tetrachloride, are preferable. These titanium compounds may be used alone or in combination of two or more kinds.

Further, (a) the electron donor used in the preparation of the solid catalyst component is an organic compound containing oxygen, nitrogen, phosphorus, sulfur, silicon, etc., and is basically a regularity in the polymerization of propylene. Is used to improve. Examples of such electron donors include esters, thioesters, amines, amides, ketones,
Examples thereof include nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides, aldehydes and organic acids.

Specifically, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyl. Organosilicon compounds such as trimethoxysilane and benzyltrimethoxysilane, dimethylphthalate, diethylphthalate, dipropylphthalate, diisobutylphthalate, methylethylphthalate, methylpropylphthalate, methylisobutylphthalate,
Ethyl propyl phthalate, ethyl isobutyl phthalate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl propyl terephthalate, methyl isobutyl terephthalate, ethyl propyl terephthalate, ethyl isobutyl terephthalate, propyl isobutyl terephthalate, dimethyl Such as isophthalate, diethyl isophthalate, dipropyl isophthalate, diisobutyl isophthalate, methyl ethyl isophthalate, methyl propyl isophthalate, methyl isobutyl isophthalate, ethyl propyl isophthalate, ethyl isobutyl isophthalate and propyl isobutyl isophthalate Aromatic dicarboxylic acid diester, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate , Ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl toluate, amyl toluate, Mention may be made of monoesters such as ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate and ethyl naphthoate.

Further, esters having 2 to 18 carbon atoms such as r-valerolactone, coumarin, phthalide and ethylene carbonate, organic acids such as benzoic acid and p-oxybenzoic acid, succinic anhydride, benzoic anhydride and p-anhydride. Acid anhydrides such as toluic acid, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone and other ketones having 3 to 15 carbon atoms, acetaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthyl aldehyde, etc. 2-1
5 aldehydes, acetyl chloride, benzyl chloride, toluyl chloride, anisyl chloride, and other acid halides having 2 to 15 carbon atoms, methyl ether, ethyl ether, isopropyl ether, n-butyl ether,
C2-C20 symmetrical or asymmetrical ethers such as t-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether, acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide, tributylamine,
N, N'-dimethylpiperazine, tribenzylamine,
Amines such as aniline, pyridine, picoline and tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile and tolunitrile, 2,2′-azobis (2-methylpropane), 2,2′-azobis (2
-Ethylpropane), 2,2'-azobis (2-methylpentane), α, α'-azobisisobutyronitrile,
A sterically hindering substituent is present on the azo bond of 1,1′-azobis (1-cyclohexanecarboxylic acid), (1-phenylmethyl) -azodiphenylmethane, 2-phenylazo-2,4-dimethyl-4-trioxypentanenitrile, etc. Examples include azo compounds formed by combining these, and these are 1
One kind may be used, or two or more kinds may be used in combination.

Among these, esters, ethers,
Ketones and acid anhydrides are preferred, especially phthalic acid di-
Aromatic dicarboxylic acid diesters such as n-butyl and diisobutyl phthalate, benzoic acid, p-methoxybenzoic acid,
Preferable are alkyl esters having 1 to 4 carbon atoms of aromatic monocarboxylic acids such as p-ethoxybenzoic acid and toluic acid. Aromatic dicarboxylic acid diesters are particularly preferable because they improve the catalytic activity and activity persistence, and increase the stereoregularity of the resulting polymer.

The solid catalyst component (a) can be obtained by a known method (JP-A-53-43094, JP-A-55-13510).
No. 2, JP-A-55-135103, JP-A-5
No. 6-18606), for example, (1) a magnesium compound or a complex compound of a magnesium compound and an electron donor is pulverized in the presence of an electron donor and a pulverization aid optionally used to give a titanium compound. A method of reacting with a liquid compound of a magnesium compound having no reducing ability and a liquid titanium compound in the presence of an electron donor to precipitate a solid titanium complex, (3) A method of reacting the titanium compound with the one obtained in (1) or (2), and (4) a method of further reacting the electron donor and a titanium compound with the one obtained in (1) or (2) above. (5) Grinding a magnesium compound or a complex compound of a magnesium compound and an electron donor in the presence of an electron donor, a titanium compound, and a grinding aid optionally used. After the method of treating with a halogen or halogen compound, (6) the (1) to (4)
It can be prepared by a method of treating the compound obtained in 1 above with halogen or a halogen compound.

Further, other methods (Japanese Patent Laid-Open No. 56-
166205, JP-A-57-63309,
JP-A-57-190004, JP-A-57-300
No. 407, JP-A-58-47003), the solid catalyst component (a) can be prepared.

Further, at least one kind of oxides of elements belonging to Groups II to IV of the periodic table, for example, oxides of silicon oxide, magnesium oxide, aluminum oxide or the like, or oxides of elements belonging to Groups II to IV of the periodic table is used. A complex oxide containing, for example,
The solid substance obtained by supporting the magnesium compound on silica alumina or the like, the electron donor and the titanium compound are contacted in a solvent at a temperature in the range of 0 to 200 ° C., preferably 10 to 150 ° C. for 2 minutes to 24 hours. By
(Ii) A solid catalyst component can be prepared.

In preparation of the (a) solid catalyst component, an organic solvent inert to the magnesium compound, the electron donor and the titanium compound as a solvent, for example, an aliphatic hydrocarbon such as hexane and heptane, benzene, Aromatic hydrocarbons such as toluene, or halogenated hydrocarbons such as mono- or polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms can be used. .

Regarding the composition of the solid catalyst component (a) thus prepared, the magnesium / titanium atomic ratio is usually 2 to 100 and the halogen / titanium atomic ratio is 5 to 20.
0, and the electron donor / titanium molar ratio is in the range of 0.1 to 10.

In the above catalyst, the organoaluminum compound used as the component (b) is represented by the general formula: AlR ³ _p X _3-p ... [I] (wherein R ³ is an alkyl group having 1 to 10 carbon atoms, X is Is a halogen atom such as chlorine or bromine, and p is a number of 1 to 3).

Examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum mono. Dialkylalkyl monohalides such as chloride and dioctylaluminum monochloride, and alkylaluminum sesquihalides such as ethylaluminum sesquichloride can be preferably used. These aluminum compounds may be used alone or in combination of two or more.

Further, the alkoxy group-containing aromatic compound used as the component (c) has the following general formula [II]

[Chemical 1] What is represented by is preferable.

In the above general formula [II], R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² is 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 n. Is 0
Alternatively, it is an integer of 1 to (6-m).

Examples of the alkoxy group-containing aromatic compound represented by the above general formula [II] include m-methoxytoluene, o-methoxyphenol, m-methoxyphenol, 2-methoxy-4-methylphenol, vinyl anisole, p- (1-propenyl) anisole, p-allylanisole, 1,3-bis (p-methoxyphenyl)
Monoalkoxy compounds such as 2-1-pentene, 5-allyl-2-methoxyphenol, 4-allyl-2-methoxyphenol, 4-hydroxy-3-methoxybenzyl alcohol, methoxybenzyl alcohol, nitroanisole and nitrophenetol, Dialkoxy compounds such as o-dimethoxybenzene, m-dimethoxybenzene, p-dimethoxybenzene, 3,4-dimethoxytoluene, 2,6-dimethoxyphenol, 1-allyl-2,4-dimethoxybenzene and 2,3,5 -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-
Examples thereof include trialkoxy compounds such as propenyl) benzene, 1,2,3-trimethoxybenzene, and 1,2,4-trimethoxybenzene. Among these, dialkoxy compounds and trialkoxy compounds are preferable. These alkoxy group-containing compounds may be used alone or in combination of two or more.

Examples of the electron donor used as the component (d) or the component (IV) include the same electron donors as those mentioned in the preparation of the solid catalyst component (a). ) The same as or different from the electron donor used in the preparation of the solid catalyst component can be used. However, the electron donor used as the component (d) needs to have a melting point of 100 ° C. or higher.

Next, as the organoaluminum compound used as the component (II) of the catalyst, the same organoaluminum compounds as those mentioned above as the component (b) can be mentioned. The same as or different from can be used.

Further, examples of the alkoxy group-containing aromatic compound used as the component (III) of the catalyst include the same alkoxy group-containing aromatic compounds as the above-mentioned component (C). The same or different one as the used alkoxy group-containing aromatic compound can be used.

To produce the soft polypropylene resin of the present invention, the catalyst component is added to the reaction system, and then propylene is introduced into this system. The catalyst components may be mixed in a predetermined amount and brought into contact with each other, and then propylene may be immediately introduced to initiate polymerization.
After aging for about 3 hours, propylene may be introduced and polymerized.

The propylene raw material may be used alone or, if desired, may be used in combination with another α-olefin. In this case, the other α-olefin is 40% of the total monomers. It is desirable that the content is not more than wt%, preferably not more than 30 wt%. As the other α-olefin, other than propylene having 2 to 30 carbon atoms, for example, ethylene, butene-1, pentene-1, hexene-
1, heptene-1, octene-1, nonene-1, decene-1, dodecene-1, tetradecene-1, octadecene-1,4-methylpentene-1,4-methylhexene-
1,4,4-dimethylpentene-1 or the like can be used. These α-olefins may be used alone or in combination of two or more.

In this way, the intrinsic viscosity [η] was 1.2 dl / by the gas-phase one-step polymerization method or the slurry one-step polymerization method.
Boiling heptane-soluble polypropylene 10 to 90 g or more
% By weight, and (b) the intrinsic viscosity [η] is 0.5 to 9.0 dl.
A soft polypropylene resin according to the invention consisting of 90 to 10% by weight of boiling heptane-insoluble polypropylene 90 g / g is obtained.

In the soft polypropylene resin of the present invention, various additives, reinforcing materials, fillers such as heat stabilizers, antioxidants, light stabilizers, antistatic agents, lubricants, nucleating agents and flame retardants can be added, if desired. , Pigments and dyes, glass fibers, carbon fibers, calcium carbonate, calcium sulfate, mica, talc, clay and the like can be added within a range not impairing the object of the present invention. Further, other thermoplastic resins, thermoplastic elastomers, rubbers and the like can be blended as required.

The thus obtained soft polypropylene of the present invention can be used for various purposes by obtaining various molded products by a commonly used molding method. When injection molding is used, it is suitable for automobile exterior parts because of its softness, good coatability, moldability, scratch resistance, and low temperature impact resistance. Specifically, bumpers, moldings, mudguards for painting, side shields, spoilers, etc.

In the case of hollow molding, it is suitable for a portion which is apt to have an uneven thickness in conventional polypropylene, for example, a bellows of a duct or the like, by utilizing good molding property. It is also suitable as a material for deep drawing. When using extrusion molding,
It is used for engine undercover sheets, etc., due to its good impact resistance and heat resistance. Further, it is suitably used for automobile interior parts because of its good workability and soft feel. For example, a ceiling material, a lining of a luggage compartment, an instrument panel skin material, and the like. In addition, the insulating sheet and heat resistance in the field of weak electrical components, which utilizes workability and insulation,
It is also used for flexible cords, booster cables, etc. in the field of electric cables utilizing weather resistance and wear resistance. In addition, in the field of civil engineering and building materials, it is also used as a waterproof sheet, a waterproof material, and a joint material. By laminating with other resin, it is possible to obtain a sheet that can satisfy various purposes.

Next, one example of the method for producing the soft polypropylene resin of the present invention by the gas-phase one-step polymerization method and one example of the method for the slurry one-step polymerization method are shown in the flow charts of FIGS. 1 and 2, respectively. Show. The production of the soft polypropylene resin by the one-step slurry polymerization method can also be carried out by the method shown in the flowchart of FIG.

[0053]

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 solid catalyst component In a glass three-necked flask having an inner volume of 500 ml, which had been sufficiently replaced with nitrogen, 20 ml of purified heptane and Mg (OEt) ₂
4 g and 1.2 g of di-n-butyl phthalate were added, the system temperature was maintained at 90 ° C., and 4 ml of TiCl ₄ was added while stirring.
After the dropping, 111 ml of TiCl ₄ was additionally added, the temperature was raised to 110 ° C., the reaction was performed for 2 hours, and then 8
It was washed with 100 ml of purified heptane at 0 ° C. 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 (I) 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, A
After adding 0.07 mol of 1 Et ₃ , 0.05 mmol of diphenyldimethoxysilane (DPDMS) and 120 g of the solid catalyst component obtained in (1) above, the system was kept at 30 ° C. and propylene was continuously added while stirring. The internal pressure was maintained at 0.5 kg / cm ² · G. After continuing this reaction for 1 hour, the solid component (I) was prepared by washing 5 times with 1 liter of purified heptane.

(3) Gas-phase one-step polymerization In a pressure-resistant stainless steel autoclave of 5 liters, 20 g of polypropylene powder and 3 mmol of AlEt ₃ were added to 1 mol.
-Allyl-3,4-dimethoxybenzene (ADMB) 0.15 mmol, diphenyldimethoxysilane (DPD)
MS) 0.23 mmol and solid component (I) 100 mg
After adding 20 ml of a heptane solution containing (0.06 mmol in terms of Ti atom) and evacuating the system for 5 minutes, while supplying propylene gas until the total pressure reaches 28 kg / cm ² · G, 70 ° C After 1.7 hours for gas phase polymerization, M
640 g of a soft polypropylene resin having an I of 0.27 was obtained. This resin has an HSP (boiling heptane solubles) content of 3
5% by weight, the intrinsic viscosity [η] of the HSP is 1.95 dl /
The HIP (boiling heptane insoluble matter) content was 65% by weight, and the intrinsic viscosity [η] of the HIP was 4.78 dl / g. Furthermore, in the pentad fraction by ¹³ C-NMR, rrrr / 1-mmmm was 34.5%, and the melting peak temperature (Tm) and the melting enthalpy (ΔH) measured by DSC were 158 ° C. and 62.6 J / g, respectively. Yes, and a domain structure was observed in a transmission electron microscope. The results are shown in Table 1.

Examples 2 to 4 and 7 In order to obtain a predetermined ratio of HSP part and HIP part,
Example 10 except that the ADMB / DPDMS ratio was changed.
A soft polypropylene resin was produced in the same manner as in. The results are shown in Table 1.

Example 5 In the same manner as in Example 1, a solid catalyst component and a solid component (I) were prepared. 5 liters of stainless steel pressure resistant autoclave, polypropylene powder 20
g, in terms of AlEt ₃ in 3m mol, 1-allyl-3,4-dimethoxybenzene (ADMB) 0.15m mol and the solid component (I) 100mg (Ti atom 0.06
Add 20 ml of heptane solution containing
After evacuating for a minute, gas phase polymerization was carried out at 50 ° C. for 1.7 hours while supplying propylene gas until the total pressure became 20 kg / cm ² · G, to obtain 350 g of a soft polypropylene resin having MI of 0.10. . The HSP (boiling heptane-soluble content) content of this resin was 41% by weight, the intrinsic viscosity [η] of the HSP was 2.98 dl / g, and the HIP (boiling heptane-insoluble content) content was 59% by weight. The intrinsic viscosity [η] was 6.14 dl / g. Further ¹³ C-NM
Pentad fraction by R, rrrr / 1-mm
mm is 29.8%, and the melting peak temperature (Tm) and melting enthalpy (ΔH) measured by DSC are 1 respectively.
It was 58 ° C. and 54.1 J / g, and a domain structure was observed in the observation with a transmission electron microscope. The results are shown in Table 1.

Example 6 A soft polypropylene resin was produced in the same manner as in Example 1 except that the amount of cocatalyst at the time of polymerization was changed so that the intrinsic viscosity [η] of the HSP part became a predetermined value. . The results are shown in Table 1.

Comparative Examples 1 to 3 In order to obtain a predetermined ratio of HSP part and HIP part,
A polypropylene resin was produced in the same manner as in Example 1 except that the amount of cocatalyst at the time of polymerization was changed so that the intrinsic viscosity [η] of the HSP part became a predetermined value. The results are shown in Table 1.

The physical properties of the polymers obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were measured as follows. (1) Intrinsic viscosity [η] Measurement was carried out in a decalin solution at a temperature of 135 ° C. (2) DS using Tm and ΔH Perkin-Elmer DSC-7
C measurement is performed to determine the peak temperature Tm of the melting peak in accordance with JIS K-7121, and JIS K-
Based on 7122, the total heat energy amount ΔH (melting enthalpy) absorbed during crystal melting was determined. (3) Domain structure Using a JEM-100CX transmission electron microscope (manufactured by JEOL Ltd.), a sample prepared by the RuO ₄ staining method and the ultrathin section method had an acceleration voltage of 100 kV and a magnification of 1000.
The domain structure was observed under the condition of -60,000. (4) rrrr / 1-mmmm JNM-FX-200 (manufactured by JEOL Ltd., ¹³ C-nuclear resonance frequency 50.1 MHz), measurement mode: complete proton decoupling method, pulse width: 6.9 μs (45
°), pulse repetition time: 3s, number of integrations: 1000
0 times, solvent: 1,2,4-trichlorobenzene / heavy benzene (90/10 Vol%), sample concentration: 250 mg /
2.5 C solvent, measurement temperature: 130 ° C, ¹³ C
-By NMR measurement, due to the difference in chemical shift due to stereoregularity of the methyl group, that is, 22.5 to 1
The pentad fraction was measured from the area intensity ratio of each peak of mmmm to mrrm appearing in the 9.5 ppm region, and rrr was measured.
r / 1-mmmm was determined.

The chemical shift of the methyl group in each atmosphere using tetramethylsilane as the standard substance is as follows. mmmm: 21.86 ppm mmmr: 21.62 ppm mmrr: 21.08 ppm mmrm + rrmr: 20.89 ppm rrrr: 20.36 ppm mrrm: 19.97 ppm

[0062]

[Table 1]

[0063]

According to the present invention, propylene is polymerized by a gas-phase one-step polymerization method or a slurry one-step polymerization method using a specific catalyst system, so that it is possible to perform cross-linking treatment.
A cost-effective soft polypropylene resin having mechanical properties comparable to those of a partially crosslinked olefinic thermoplastic elastomer (TPO) is obtained. The soft polypropylene resin of the present invention has excellent melting characteristics, and not only extrusion moldability but also good injection moldability, such as a bumper in the automobile field, a sheet for construction materials in the field of construction and construction, and a waterproof material. It is suitable for use as a material.

[Brief description of drawings]

FIG. 1 is a flow chart of an example of a method for producing a soft polypropylene resin of the present invention by a gas-phase one-step polymerization method.

FIG. 2 is a flow chart of an example of a method for producing a soft polypropylene resin according to the present invention by a slurry one-step polymerization method.

FIG. 3 is a flow chart of a different example of a method for producing a soft polypropylene resin according to the present invention by a slurry one-step polymerization method.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akinobu Sugawara 1 Inezaki Kaigan, Ichihara City, Chiba Idemitsu Petrochemical Co., Ltd.

Claims (2)

[Claims] 1. A soft polypropylene resin obtained by a gas phase one-step polymerization method or a slurry one-step polymerization method, comprising:
(A) 10 to 90% by weight of boiling heptane-soluble polypropylene having an intrinsic viscosity [η] of 1.2 dl / g or more, (b)
A soft polypropylene resin composed of boiling heptane-insoluble polypropylene 90 to 10% by weight having an intrinsic viscosity [η] of 0.5 to 9.0 dl / g. 2. In the pentad fraction by ¹³ C-nuclear magnetic resonance absorption method, rrrr / 1-mmmm is 20% or more, and the melting peak temperature (Tm) and the melting enthalpy (determined by differential scanning calorimetry) ΔH) is 150 ° C. or higher and 100 J / g or lower, respectively.
The described soft polypropylene resin.