JP3210155B2 - Method for producing thermoplastic polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a four-stage polymerization of a thermoplastic polymer consisting of a propylene homopolymer, two types of ethylene-propylene random copolymer and an ethylene-butene random copolymer. It has good workability during injection molding and good appearance, excellent flexural modulus, surface hardness, impact resistance, and paintability.
For example, the present invention relates to a method for producing a specific thermoplastic polymer suitable for injection molded articles such as automobile parts.

[0002]

2. Description of the Related Art Thermoplastic polymers used in the field of industrial parts such as automobiles are required to have excellent properties such as rigidity, scratch resistance, impact resistance and paintability. Since the quality balance is generally insufficient, the quality has been improved by blending various rubber components.

However, since it is economically disadvantageous to blend expensive rubber components, many attempts have been made to improve the quality balance of thermoplastic polymers by carrying out polymerization in three stages. (Japanese Unexamined Patent Publication No.
-50909, JP-A-58-40314 and JP-A-57-67611. However, as far as the present inventors know, although the quality is improved to some extent by these methods, none of the techniques is sufficient to meet the recently required high quality.

[0004]

In many of such conventional thermoplastic polymers, the propylene homopolymer portion does not always have a sufficiently high crystallinity or the copolymer rubber portion has an insufficient strength. Because of this, the rigidity, scratch resistance, and impact resistance are unsatisfactory, and because the compatibility of the propylene homopolymer portion and the copolymer rubber portion is low, the dispersion state of the copolymer rubber portion is rough. In addition, impact resistance and paintability were insufficient.

An object of the present invention is to solve these problems comprehensively and obtain an economically advantageous thermoplastic polymer and its composition.

[0006]

[Means for Solving the Problems]

[Summary of the Invention] <Summary> The present invention is based on the discovery that a specific four-stage polymerization method can provide a thermoplastic polymer having an extremely excellent quality balance.

That is, the method for producing a thermoplastic polymer according to the present invention comprises a step of bringing an olefin into contact with a stereoregular catalyst to carry out polymerization, and this polymerization step includes the following polymerization steps (1) to (4). Is a feature. (However, in the range polymerization ratio of 1/2 to 2 with produced polymer by the generated polymer and polymerization process by polymerization step (3) (4), the polymerization step (1) to the polymerization Engineering
The total of the polymers produced in step (4) is 100% by polymerization.
Is ). Polymerization Step (1) Homopolymerization of propylene is performed to obtain a density of 0.908 g.
/ Cm ³ or more to produce a homopolymer of propylene (however, the polymerization amount in this step is 50 to 7 of the total polymerization amount)
0% by weight). Polymerization step (2) Ethylene / propylene reaction ratio is 30 / 70-50 / 50
(Weight ratio) by supplying an ethylene / propylene mixture to the polymerization system to form an ethylene-propylene copolymer (however, the polymerization amount in this step is 2 to 10% by weight of the total polymerization amount). Corresponding amount). Polymerization step (3) Ethylene / propylene reaction ratio is 90/10 to 70/30
(Weight ratio) to supply an ethylene / propylene mixture to the polymerization system to produce an ethylene-propylene copolymer (however, the polymerization amount in this step is 8 to 25% by weight of the total polymerization amount). Corresponding amount). Polymerization Step (4) A step of supplying an ethylene / butene mixture to a polymerization system so that an ethylene / butene reaction ratio becomes 90/10 to 70/30 (weight ratio) to form an ethylene-butene copolymer (however, The polymerization amount in this step is an amount corresponding to 8 to 25% by weight of the total polymerization amount).

Further, the thermoplastic polymer composition according to the present invention has an MFR produced by the above method of 10 to 100.
g / 10 minutes of thermoplastic polymer 100 parts by weight and talc 7
-25 parts by weight. <Effect> The thermoplastic polymer obtained by the present invention and the thermoplastic polymer composition obtained by adding talc to the thermoplastic polymer have good workability and good appearance during injection molding, and have a flexural modulus, tensile elongation property, and surface. It is excellent in hardness, impact resistance and paintability, and is suitable for injection molded articles such as automobile parts.

Further, the composition according to the present invention has a high crystallinity as compared with the conventional thermoplastic polymer composition, so that the cooling solidification rate is high, and therefore the cooling time during injection molding is shortened. Therefore, the production speed of the molded article can be greatly improved.

Specifically, the thermoplastic polymer composition according to the present invention has good moldability, a flexural modulus of 10,000 kg / cm ² or more, and a tensile elongation at break of ² kg.
100% or more, Rockwell hardness is 50 or more, Izod value at -30 ° C is 5Kg · cm / cm ² or more, and peel strength of coated film after coating is 700g / cm or more. As it is, since the molding processability is good, a molded article having improved rigidity and scratch resistance can be provided.

[0011] Since this composition has such excellent properties, it is required to be applied to various applications, particularly to bumpers, air dam spoilers, fascias, etc., and particularly to injection molding in which rigidity and scratch resistance are important. The present invention can be applied to a large-sized automobile exterior member, and in this case, the effect of the present invention is greatly exerted. [Specific description of the invention] <Stereoregular catalyst> The stereoregular catalyst used in the present invention comprises a titanium-containing solid catalyst component and an organoaluminum compound, and belongs to the so-called Ziegler catalyst category. . Here, “consisting of” does not mean that the components are only the titanium-containing solid catalyst component and the organoaluminum compound component,
It does not preclude the coexistence of other ingredients where appropriate.

In the present invention, any stereoregular catalyst can be used without departing from the spirit of the present invention. For example, a catalyst comprising a titanium-containing solid catalyst component and an organoaluminum compound component as described below is preferable.

Titanium-containing solid catalyst component The titanium component of the titanium-containing solid catalyst component includes, for example, TiCl ₃ compounds, such as those reduced by H _2, reduced by metallic aluminum, reduced by organoaluminum, and the like.
There are various TiCl ₃ compounds. In addition, the above TiCl
_{The three} compounds may be obtained by adding mechanical pulverization. Also,
TiCl _{3 obtained} by reducing TiCl ₄ or the like with organoaluminum
Can be further treated with an electron donating compound, and if necessary, a compound treated with TiCl ₄ can be used.

Further, the titanium component can be used as a so-called highly active catalyst supported on a magnesium compound or the like (the titanium component is used for a Ziegler type catalyst containing titanium, magnesium and halogen). Can be defined as a solid component).

More specifically, for example, in the present invention, JP-A-53-45688, JP-A-54-3894, and JP-A-54-3894
Nos. 1092, 54-39483, 54-9449
No. 1, No. 54-118484, No. 54-131589
Nos. 55-75411, 55-90510, 55-90511, 55-127405, and 55
-147507, 55-155003, 56-
No. 18609, No. 56-70005, No. 56-720
No. 01, No. 56-86905, No. 56-90807
Nos. 56-155206, 57-3803, 57-34103, 57-92007, 57-
No. 121003, No. 58-5309, No. 58-531
No. 0, No. 58-5311, No. 58-8706, No. 5
8-27732, 58-32604, 58-3
No. 2605, No. 58-67703, No. 58-1172
No. 06, No. 58-127708, No. 58-18370
No. 8, No. 58-183709, No. 59-149905
And those described in JP-A-59-149906.

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 raised. Among these magnesium compounds, magnesium dihalide is preferable.

The titanium compound serving as a titanium source has a general formula of Ti (OR ¹ ) _4-n X _n (where R ¹ is a hydrocarbon residue, and preferably has about 1 to 10 carbon atoms). , X represents a halogen, and n represents a number satisfying 0 ≦ n ≦ 4.). As a specific example, TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) Cl
₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ )
₃ Cl, Ti (O-iC ₃ H ₇ ) Cl ₃ , Ti (On
_{C 4 H 9) Cl 3,} Ti (O-nC 4 H 9) 2 Cl 2,
Ti (OC ₂ H ₅ ) Br ₃ , Ti (OC ₂ H ₅ ) (OC
_{4 H 9) 2 Cl, Ti} (O-nC 4 H 9) 3 Cl, Ti
_{(O-C 6 H 5)} Cl 3, Ti (O-iC 4 H 9) 2 C
l ₂ , Ti (OC ₅ H ₁₁ ) Cl ₃ , Ti (OC ₆ H ₁₃ )
Cl ₃ , Ti (OC ₂ H ₅ ) ₄ , Ti (O-nC
_{3 H 7) 4, Ti (} O-nC 4 H 9) 4, Ti (O-i
_{C 4 H 9) 4, Ti} (O-nC 6 H 13) 4, Ti (O-
nC ₈ H ₁₇ ) ₄ , Ti [OCH ₂ CH (C ₂ H ₅ ) C ₄
H ₉ ] _{4 and the} like.

A molecular compound obtained by reacting TiX ' ₄ (here, X' represents a halogen) with an electron donor described later can also be used. Specific examples of such molecular compounds include TiCl ₄ .CH ₃ COC ₂ H ₅ , TiC
_{l 4 · CH 3 CO 2 C} 2 H 5, TiCl 4 · C 6 H 5 N
O ₂ , TiCl ₄ .CH ₃ COCl, TiCl ₄ .C _{6
H 5 COCl, TiCl 4 · C} 6 H 5 CO 2 C 2 H 5,
TiCl ₄ .ClCOC ₂ H ₅ , TiCl ₄ .C ₄ H ₄
O and the like.

Among these titanium compounds, preferred are TiCl ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC
₄ H ₉₎ is _{4, Ti (OC 4 H 9} ) Cl 3 , etc..

The general formula Ti (OR ² ) _3-m X _m (where R ² is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X represents a halogen, m represents a number satisfying 0 <m ≦ 3). Specific examples include TiCl ₃ , TiBr ₃ , Ti
(OCH ₃ ) Cl ₂ , Ti (OC ₂ H ₅ ) Cl _{2 and the} like.

Further, titanocene compounds such as dicyclopentadienyldichlorotitanium, dicyclopentadienyldimethyltitanium and bisindenyldichlorotitanium can be used.

The halogen source is usually supplied from the above-mentioned halogen compounds of magnesium and / or titanium, but other halogen sources such as aluminum halides, silicon halides and phosphorus halides Such as known halogenating agents.

The halogen contained in the catalyst component is fluorine,
May be chlorine, bromine, iodine or a mixture thereof,
Particularly, chlorine is preferred.

The solid components used in the present invention include, in addition to the above essential components, silicon compounds such as SiCl ₄ and CH ₃ SiCl ₃ , polymer silicon compounds such as methyl hydrogen polysiloxane, Al (OiC ₃ H ₇ ) ₃ , AlCl ₃ ,
AlBr ₃ , Al (OC ₂ H ₅ ) ₃ , Al (OCH ₃ )
Aluminum compound such as ₂ Cl and B (OC
Other components such as boron compounds such as H ₃ ) ₃ , B (OC ₂ H ₅ ) ₃ and B (OC ₆ H ₅ ) ₃ can be used, and these are solid components such as silicon, aluminum and boron. It can be left inside.

Further, in producing this solid component, an electron donor can be used as an internal donor.

Electron donors (internal donors) that can be used for producing the solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, and acid amides. Oxygen-containing electron donors such as carboxylic acids and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amine, nitrile and isocyanate.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol,
Octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol and isopropylbenzyl alcohol, (ii) phenol, cresol, xylenol, ethyl phenol,
C6 to C25 phenols which may have an alkyl group, such as propylphenol, cumylphenol, nonylphenol, and naphthol; and (C) C3 to C15 phenols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone. Ketones, (d) acetaldehyde, propionaldehyde,
C2 to C15 aldehydes such as octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, methyl (fo) formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, propionic acid ethyl,
Methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoic acid Octyl, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate,
C2-C2 such as diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate, etc.
Organic acid esters 0, (f) inorganic acid esters such as silicates such as ethyl silicate, butyl silicate and phenyltriethoxysilane, (g) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid C2 to C15 acid halides such as chloride, phthaloyl chloride and phthaloyl oxide; and C2 to C2 such as (thi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether.
0 ethers, (li) acetic acid amide, benzoic acid amide,
Acid amides such as toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, amines such as aniline, pyridine, picoline, tetramethylethylenediamine, (l) acetonitrile, benzonitrile, And nitriles such as tolunitrile. Two or more of these electron donors can be used. Preferred among these are organic acid esters and acid halides, particularly preferred are phthalic acid esters,
Cellosolve acetate and phthalic halide.

The amount of each of the above components may be any as long as the effects of the present invention are recognized.
The following range is preferred.

The titanium compound is used in a molar ratio of 1 × 10 ^-4 to 1 with respect to the magnesium compound used.
000, preferably 0.01 to 10. When a compound for that purpose is used as a halogen source, the amount used is 1 × 10 5 in molar ratio with respect to the amount of magnesium used irrespective of whether the titanium compound and / or the magnesium compound contains halogen or not. The range is preferably from ^{-2 to} 1000, and more preferably from 0.1 to 100.

The amount of silicon, aluminum and boron used is preferably in the range of 1 × 10 ^{−3 to} 100, and more preferably in the range of 0.01 to 1 in a molar ratio to the amount of the magnesium compound. is there.

The amount of the electron donating compound when used is
The molar ratio of the magnesium compound is 1 to the amount used.
× 10 ^-3 to 10 is good, preferably 0.01 to 10
5 is within the range.

The titanium component used in the present invention can be produced, for example, by the following production method using the above-mentioned titanium source, magnesium source and halogen source, and if necessary, other components such as an electron donor. Can be. (A) A method in which a magnesium halide is brought into contact with an electron donor, if necessary, and a titanium-containing compound. (B) A method in which alumina or magnesia is treated with a phosphorus halide compound, and the resulting mixture is brought into contact with a magnesium halide, an electron donor, and a titanium halide-containing compound. (C) A method of 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.

As the polymer silicon compound, a compound represented by the following formula is suitable.

[0034]

Embedded image (Where R is a hydrocarbon residue having about 1 to 10 carbon atoms, p
Indicates the degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes.) Of these, methylhydrogenpolysiloxane, ethylhydrogenpolysiloxane, phenylhydrogenpolysiloxane, cyclohexylhydrogenpolysiloxane Preferred are siloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, and the like. (D) A method in which a magnesium compound is dissolved in a titanium tetraalkoxide and an electron donor, and the solid component precipitated with a halogenating agent or a titanium halide compound is brought into contact with the titanium compound. (E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, and the like, and then, if necessary, is contacted with an electron donor titanium compound. (F) A method of contacting an alkoxymagnesium compound with a halogenating agent and / or a titanium compound in the presence or absence of an electron donor.

Thus, titanium, magnesium,
And a titanium component containing halogen.

In the present invention, the following silicon compounds and organometallic compounds of metals of Groups I to III of the periodic table can be used, if necessary.

[0037] As silicon compounds which can be used in the present invention have the general formula _{^{R 3 R 4 3-q Si}} (OR 5) q ( provided that, ^{R 3} is a branched chain hydrocarbon residue or a cycloaliphatic hydrocarbon residue , R ⁴ is a hydrocarbon residue the same as or different from R ³ , R ⁵ is a hydrocarbon residue, and q is a number satisfying 1 ≦ q ≦ 3).
It goes without saying that the silicon compound may be a mixture of plural kinds of the compounds of the formula.

Here, R ³ is preferably branched from a carbon atom adjacent to a silicon atom. In this case, the branching group may be an alkyl group, a cycloalkyl group or an aryl group (for example, a phenyl group or a methyl-substituted phenyl group).
It is preferred that More preferred R ³ is one in which the carbon atom adjacent to the silicon atom, ie, 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. The number of carbon atoms of R ³ is usually 3 to 20, preferably 4 to 10 in the case of a branched hydrocarbon residue, and usually 5 to 20, preferably 6 in the case of R ³ is a cyclic aliphatic hydrocarbon residue. -10.

R ⁴ has 1 to 20 carbon atoms, preferably 1 to
It is usually 10 branched or straight-chain aliphatic hydrocarbon groups. R ⁵ is an aliphatic hydrocarbon group, preferably usually be a chain aliphatic hydrocarbon group having 1 to 4 carbon atoms.

Specific examples of the silicon compound that can be used in the present invention are as follows. (CH ₃ ) ₃ CSi (CH ₃ )
(OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ )
_{2) (OCH 3) 2,} (CH 3) 3 CSi (CH 3)
(OC ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₃ CSi (CH ₃ )
(OCH ₃ ) ₂ , (CH ₃ ) (C ₂ H ₅ ) CHSi (C
H ₃ ) (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CHCH ₂ ) ₂
Si (OCH ₃ ) ₂ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi
(CH ₃ ) (OCH ₃ ) ₂ , (C ₂ H ₅ ) (CH ₃ ) ₂
CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CS
i (OCH ₃ ) ₃ , (iC ₃ H ₇ ) ₂ Si (OCH ₃ )
₂ , (iC ₃ H ₇ ) ₂ Si (OC ₂ H ₅ ) ₂ , (iC ₃
H ₇ ) (CH ₃ ) Si (OCH ₃ ) ₂ , (CH ₃ ) ₃ C
Si (OC ₂ H ₅ ) ₃ , (C ₂ H ₅ ) ₃ CSi (OC _{2
H 5) 3, (CH 3} ) (C 2 H 5) CHSi (OC
H ₃ ) ₃ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (OC
H ₃ ) ₃ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (OC ₂ H
₅ ) ₃ ,

[0041]

Embedded image Among these, preferred are a branched or branched hydrocarbon residue having 3 to 20 carbon atoms and a cycloaliphatic hydrocarbon residue having 5 to 12 carbon atoms, wherein the carbon at the α-position of R ³ is secondary or tertiary. So,
Particularly, it is a silicon compound having a branched hydrocarbon residue having 4 to 10 carbon atoms in which the carbon at the α-position of R ³ is tertiary.

The amount of the silicon compound used may be any amount as long as the effects of the present invention are recognized, but is generally in the range of 0.1 to 0.1 in the atomic ratio of titanium to silicon (silicon / titanium).
It is good to be in the range of 01-1000, preferably 0.1-1.
00 range.

The organometallic compounds of metals of Groups I to III of the Periodic Table used as required in the present invention have at least one organic group-metal bond. In this case, the organic group is typically a hydrocarbyl group having about 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms.

The remaining valences (if any) of the metal of the organometallic compound in which at least one of the valences is filled with an organic group are hydrogen, halogen, hydrocarbyloxy (hydrocarbyl is About 1 to 10 and preferably about 1 to 6) or the metal (specifically, methylalumoxane in the case of methylalumoxane) via an oxygen atom.

[0045]

Embedded image Others will be satisfied.

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,
Organomagnesium compounds such as tert-butylmagnesium bromide; (c) organozinc compounds such as diethylzinc and dibutylzinc; (d) trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-
Hexylaluminum, diethylaluminum chloride, diethylaluminum hydride, diethylaluminum ethoxide, ethylaluminum sesquichloride,
Organic aluminum compounds such as ethylaluminum dichloride and methylalumoxane can be mentioned. Of these, organoaluminum compounds are particularly preferred.

When the organometallic compound is used, the amount of the organometallic compound used may be any as long as the effect of the present invention is recognized, but generally, ((organometallic compound) / titanium)
At an atomic ratio of 0.01 to 100, preferably 0.1 to 3
0.

The thermoplastic polymer according to the present invention is preferably a propylene homopolymer obtained by the polymerization step (1) having a large pore volume. Therefore, the titanium-containing solid catalyst component of the stereoregular catalyst used in the present invention is obtained by converting the above-mentioned titanium component to carbon to obtain the propylene homopolymer obtained in the polymerization step (1) with a large pore volume. It is preferable to carry out prepolymerization with a diene compound of several or more.

Specific examples of the diene compound used in such a case include 1,2-butadiene, isoprene, 1,4-hexadiene, 1,5-hexadiene,
1,3-pentadiene, 1,4-pentadiene, 2,3
-Pentadiene, 2,6-octadiene, cis-2,
trans 4-hexadiene, trans 2, trans 4-hexadiene, 1,2-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene,
2,4-heptadiene, dicyclopentadiene, 1,3
-Cyclohexadiene, 1,4-cyclohexadiene,
Cyclopentadiene, 1,3-cycloheptadiene,
1,3-butadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,9-decadiene, 1,13-tetradecadiene, para-divinylbenzene, meta-divinylbenzene, Orthodivinylbenzene, dicyclopentadiene, and the like. Preferred among these are divinylbenzenes and 1,5-hexadiene.

The reaction conditions for the titanium component and the diene compound are as follows:
As long as the effects of the present invention can be recognized, any one can be used, but generally the following range is preferable.

The prepolymerization amount of the diene compound is in the range of 1 to 100 g, preferably 2 to 10 g, per gram of the titanium solid component. As the reaction conditions, the reaction temperature is -50 ° C to 150 ° C, preferably 0 ° C.
１００100 ° C. In general, the reaction is preferably performed with stirring, and at that time, the reaction may be performed in the presence of an inert solvent such as n-hexane and n-heptane.

[0052] Specific examples of the organoaluminum compound constituting the stereoregular catalysts to be used in the organic aluminum compound present invention, ^{_R 6} _3-r AlX r or ^{_{R 7 3-s Al (OR}} 8) s ( wherein, R ⁶ and R ⁷ may be the same or different and each may be a hydrocarbon residue or a hydrogen atom having about 1 to 20 carbon atoms, R ⁸ is a hydrocarbon residue having about 1 to 20 carbon atoms, X is a halogen, r and s are each 0 ≦
r <3, 0 <s <3. ). Specifically, (a) trimethylaluminum, triethylaluminum, triisobutylaluminum,
Trialkylaluminums such as trihexylaluminum, trioctylaluminum, tridecylaluminum, etc .; alkyl aluminum halides such as (ii) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride;
(C) alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; and (d) aluminum alkoxides such as diethyl aluminum ethoxide and diethyl aluminum phenoxide.

These organoaluminum compounds (a) to (d) can be used in combination. For example,
Combinations of triethylaluminum and diethylaluminum ethoxide, combinations of diethylaluminum monochloride and diethylaluminum ethoxide, combinations of ethylaluminum dichloride and ethylaluminum diethoxide, and combinations of triethylaluminum, diethylaluminum ethoxide and diethylaluminum chloride .

The amount of the organoaluminum compound used is such that the ratio of (organoaluminum compound) / (titanium component) is 0.1 to 1000, preferably 1 to 100 by weight. <Polymerization Step> The polymerization step of the present invention carried out in the presence of the catalyst component comprises four steps of specific polymerization steps (1) to (4).

Polymerization Step (1) In the polymerization step (1), propylene is homopolymerized,
A propylene homopolymer having a density of 0.908 g / cm ³ or more is produced in an amount corresponding to 50 to 70% by weight of the total polymerization amount.

The polymer obtained in the polymerization step (1) has a density of 0.908 g / cm ³ or more, preferably 0.909 g / cm ^3.
/ Cm ³ or more. If the density is less than the above, the surface hardness of the product is insufficient, which is inappropriate. The polymerization ratio in the polymerization step (1) is 50 to 70% by weight, preferably 55 to 65% by weight. If it is less than the above, the rigidity and surface hardness are insufficient, while if it is more than the above, the impact resistance and the adhesion of the coating film are insufficient.

The propylene homopolymer obtained in this polymerization step has a pore diameter of 10 as measured by a porosimeter.
The pore volume within the range of 0 to 2000 Å is 0.05 to 2.0 cm ³ / g, more preferably 0.1 to 2.0 cm ³ / g.
Those having a range of 1.0 to 1.0 cm ³ / g are preferred.

If the pore volume is outside the above range, the properties of the final copolymer deteriorate, and it may be difficult to produce the thermoplastic polymer of the present invention.

Polymerization Step (2) In the polymerization step (2), the ethylene / propylene reaction ratio is 3
0/70 to 50/50 (weight ratio), preferably 35/6
5-45 / 55 (weight ratio), ethylene /
The propylene mixture is fed to the polymerization system to produce an ethylene-propylene copolymer in an amount corresponding to 2 to 10% by weight, preferably 4 to 8% by weight of the total polymerization amount. ethylene/
If the propylene reaction ratio exceeds the above-mentioned range, the adhesion of the coating film becomes insufficient. On the other hand, if the propylene reaction ratio becomes excessive, the tensile elongation characteristics are deteriorated. On the other hand, if the polymerization ratio is less than the above, the impact resistance and tensile elongation characteristics are insufficient, and if the polymerization ratio is more than the above, the surface hardness is insufficient.

Polymerization Step (3) In the polymerization step (3), the ethylene / propylene reaction ratio is 9
0/10 to 70/30 (weight ratio), preferably 85/1
5/75/25 (weight ratio), ethylene /
The propylene mixture is fed to the polymerization system to produce an ethylene-propylene copolymer in an amount corresponding to 8 to 25% by weight, preferably 12 to 22% by weight of the total polymerization amount. When the ethylene / propylene reaction ratio becomes more than the above range, the impact resistance and the adhesion of the coating film become insufficient.
If the propylene content is excessive, the surface hardness becomes insufficient, and both are unsuitable. On the other hand, if the polymerization ratio is less than the above, the adhesion of the coating film is insufficient, and if the polymerization ratio is more than the above, the surface hardness is insufficient.

Polymerization Step (4) In the polymerization step (4), the ethylene / butene reaction ratio was 90 /
10-70 / 30 (weight ratio), preferably 85 / 15-
75/25 (weight ratio), the ethylene / butene mixture is supplied to the polymerization system, and the ethylene-butene copolymer is 8 to 25% by weight of the total polymerization amount, preferably 12 to 22%.
% By weight. If the reaction ratio of ethylene / butene is more than the above range, the impact resistance will be insufficient. On the other hand, if the butene is excessive, the surface hardness will be insufficient. On the other hand, if the polymerization ratio is less than the above, the adhesion of the coating film is insufficient, and if the polymerization ratio is more than the above, the rigidity is insufficient.

The polymerization ratio of the polymer produced in the polymerization step (3) and the polymer produced in the polymerization step (4) in the present invention is in the range of 1/2 to 2. If the polymerization ratio is less than the above, the adhesion of the coating film is insufficient, and if the polymerization ratio is more than the above, the tensile elongation characteristics are deteriorated, and both are unsuitable.

The polymerization step (1) is a step for producing isotactic polypropylene, and the polymerization steps (2) to (4) are for producing an elastomer of propylene and ethylene or butene to withstand the thermoplastic polymer. This is a step of producing a copolymer component that imparts impact properties, tensile elongation characteristics, and paintability. Therefore, in each polymerization step, a small amount of a component which can be copolymerized with propylene, ethylene or butene can be used, as long as the purpose of the present invention is not violated.

The polymerization temperature in each of the above polymerization steps is usually 30 to 90 ° C., preferably 50 to 80 ° C., and the polymerization pressure is usually in the range of 1 to 50 kg / cm ² . When a molecular weight modifier is used as desired, hydrogen is used as the molecular weight modifier. The polymerization in each step can be carried out by any of a batch system and a continuous system. At this time, there are a polymerization bulk polymerization method using the monomer used as a medium as a medium, a gas phase polymerization method using no medium, and a method of performing polymerization by combining these. The order of performing each polymerization step is arbitrary, but (1) → (2) → (3) →
It is preferable to carry out the polymerization step in the order of (4) or (1) → (2) → (4) → (3) in terms of flexural modulus and impact strength. <Thermoplastic polymer and composition> The thermoplastic polymer according to the present invention is obtained by the above-mentioned polymerization step (1).
To (4).
Therefore, such a thermoplastic polymer, when viewed structurally, is substantially the following block (A) 50 to 70% by weight,
Block (B) 2 to 10% by weight, Block (C) 8 to 2
Propylene block copolymer comprising 5% by weight and 8 to 25% by weight of block (D) (provided that block (C)
Ratio between the block (D) is in a range of 1/2 to 2,
The total of the blocks (A) to (D) is 100% by weight.
Consist in a), it is possible that. A propylene homopolymer having a block (A) density of 0.908 g / cm ³ or more (particularly preferably having a pore volume of 0.05 cm ³ / g or more in a pore diameter range of 100 to 2000 Å). Block (B) ethylene / propylene reaction ratio is 30 / 70-50 / 50
(Weight ratio) ethylene-propylene random copolymer. Block (C) ethylene / propylene reaction ratio is 90/10 to 70/30
(Weight ratio) ethylene-propylene random copolymer. Block (D) An ethylene / butene random copolymer having an ethylene / butene reaction ratio of 90/10 to 70/30 (weight ratio).

The thermoplastic polymer according to the present invention may be of any MFR. However, considering the moldability when the thermoplastic polymer is used as a molding resin, the MFR is 10 to 100 g / m. 10 minutes is preferred. If the MFR is less than the above, workability is inferior. If the MFR is more than the above, impact resistance and tensile elongation characteristics are deteriorated.

Such a thermoplastic polymer can be formed into a molded article having good properties as it is, such as flexural modulus, tensile elongation, surface hardness and impact resistance. The characteristics of the thermoplastic polymer according to the present invention can be most effectively enjoyed when an inorganic filler is added to the thermoplastic polymer. A predetermined amount of inorganic filler, especially talc (100 parts of thermoplastic polymer, preferably 7 to 25 parts by weight, more preferably 10 parts by weight)
The blended thermoplastic polymer composition has excellent workability and good appearance during injection molding, and has extremely excellent flexural modulus, tensile elongation characteristics, surface hardness, impact resistance, and paintability. It is suitable for manufacturing injection-molded articles such as automobile parts. If the amount of talc is less than the above, it is difficult to obtain a sufficient flexural modulus, and if it is more than the above, the specific gravity of the composition becomes too high and the product becomes heavy, which is not preferable. Also, talc has a particle size of 0.05 to 5
μm, especially 1 to 3 μm is preferred.

[0067]

The following examples serve to illustrate the invention.

Example 1 Preparation of Titanium-Containing Solid Catalyst Component 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then 0.4 mol of MgCl ₂ and Ti (O-nC ₄ H ₉ ) 0.8 mol of ₄ was introduced, and 9
The reaction was performed at 5 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.

Then, 50 ml of n-heptane purified in the same manner as described above was introduced into a flask sufficiently purged with nitrogen, and the solid component synthesized as above was added in an amount of 0.2 mg in terms of Mg atoms.
4 moles were introduced. Then, 0.8 mol of SiCl ₄ was mixed with 25 ml of n-heptane, 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.

Into a flask sufficiently purged with nitrogen, 50 ml of sufficiently purified n-heptane was introduced, then 5 g of the solid component obtained above was introduced, 15 g of divinylbenzene and (CH ₃ ) ₃ CSi (CH ₃ ) (OCH
₃ ) 2.6 ml of ₂ and 4.5 g of triethylaluminum were introduced, and contacted at 30 ° C. for 2 hours. After the end of the contact, wash thoroughly with n-heptane,
A titanium-containing solid component was obtained. A portion was taken out and the prepolymerization amount of divinylbenzene was examined. The prepolymerization amount was 2.64 g per gram of the titanium-containing solid component. [Polymerization] After sufficiently replacing the stirred autoclave having an inner volume of 20 liters with propylene, 3 kg of liquid propylene was introduced at 20 ° C., and then triethylaluminum 2.5 kg was added.
g and the solid catalyst component 0.5 g were introduced. The polymerization step (1) was carried out by introducing 8 Nl of hydrogen and then performing a polymerization operation at a temperature of 75 ° C. for 2 hours. When the pore volume of the obtained polypropylene powder was measured by a porosimeter, the pore volume within the range of pore diameter of 100 to 2,000 Å was 0.15 cm ³ / g.
Met. The polymerization step (2) was carried out at 65 ° C. by feeding ethylene at a feed rate of 0.36 kg / hr and ethylene at a feed rate of 0.24 kg / hr for 0.5 hour to perform ethylene-propylene copolymerization. The polymerization step (3) is 6
At 5 ° C., ethylene-propylene copolymerization was carried out by supplying propylene at a supply rate of 0.17 kg / hr and ethylene at a supply rate of 0.68 kg / hr for 1 hour.
In the polymerization step (4), butene was added at 0.17 kg /
hr and ethylene were fed at a feed rate of 0.68 kg / hr for 1 hour to carry out ethylene-butene copolymerization.

The angle of repose of the obtained product powder was 38.4.
The MFR was 21 g / 10 minutes. Table 1 shows the polymerization results.

To 100 parts by weight of this thermoplastic polymer, 15 parts by weight of talc were added, 0.1 part by weight of 2,6-di-tert-butyl-p-phenol, and tetrakis [methylene-3-
(3 ', 5'-Di-t-butyl-4'-hydroxyphenyl) propionate] Mix 0.1 part by weight of methane and 0.5 part by weight of carbon black and mix for 5 minutes with a super mixer manufactured by Kawada Seisakusho After that, Kobe Steel F
The composition was obtained by kneading and granulating at 210 ° C. using a CM twin-screw kneader.

Thereafter, various test pieces were prepared at a molding temperature of 220 ° C. using an injection molding machine having a mold clamping force of 100 tons, and the performance was evaluated according to the measuring method described later. Table 3 shows the obtained performance evaluation results.

Examples 2 to 10 and Comparative Examples 1 to 10 The same solid catalyst components as in Example 1 were used except that the monomer supply rate in each polymerization step and the hydrogen supply amount in the polymerization step (1) were changed. A four-stage polymerization process was performed in the same manner as in Example 1 to obtain a thermoplastic polymer. A stabilizer and talc were blended with the thermoplastic polymer. Tables 1 and 2 show that
The results of the polymerization are shown, and Tables 3 and 4 show the results of the performance evaluation.

COMPARATIVE EXAMPLE 11 A four-stage polymerization was carried out in the same manner as in Example 1 except that a titanium trichloride catalyst manufactured by Marubeni Solvay Co., Ltd. was used as a solid catalyst component and diethylaluminum chloride was used as an organoaluminum compound. Was similarly blended. Table 2 shows the polymerization results, and Table 4 shows
9 shows the results of performance evaluation. [Measurement Methods] Various measurement methods employed in the present invention are as follows. (1) MFR: 2.1 according to ASTM-D1238.
Measured at 230 ° C. using a 6 kg load. (2) Density: Measured at 23 ° C. according to ASTM-D1505. (3) Flexural modulus: 23 according to ASTM-D790
Measured in ° C. (4) Tensile elongation at break: measured at 23 ° C. according to ASTM-D638. (5) Surface hardness: 23 ° C. according to ASTM-D785
Was evaluated on the R-scale. (6) Impact resistance: -30 according to ASTM-D256
It evaluated by the Izod value in ° C. (7) Adhesion of the coating film: The coating film peeling strength described below was evaluated.

Coating method a. The test piece of the injection molded article is exposed to the boiling steam of 1,1,1-trichloroethane for 30 seconds, and then left to dry at room temperature for 30 minutes.

B. Next, a masking tape is stuck on the lower half, leaving the upper half of the test piece side.

C. Next, a polyuretene-modified polyolefin primer for polypropylene (trade name “SOFLEX 2500” manufactured by Kansai Paint Co., Ltd.) was spray-coated so as to have a film thickness of about 10 μm, left at room temperature for 30 minutes, dried, and then affixed with b. Peel off the masking tape.

D. Next, a one-component urethane-based top coating containing an isocyanate-based curing agent (manufactured by Nippon Bee Chemical Co., Ltd.
Spray-paint the product name “Flexen 105” to a film thickness of about 80 μm, and place in a 120 ° C. air oven for 30 minutes.
After baking for 5 minutes, it was left at room temperature for 48 hours and subjected to a coating film adhesion test.

Measurement method a. A cellophane adhesive tape is brought into close contact with the entire surface of the painted test piece, and a cut is made in a vertical direction to reach the substrate with a cutter every 10 mm from above.

B. Peel off the coating film on the side where the primer was not applied while keeping the cellophane adhesive tape in close contact,
It is bent in the direction of 180 degrees and attached to a tensile tester.

C. The test is performed at 23 ° C. at a tensile speed of 50 mm / min, and 10 peak values are read from a curve drawn on a recorder to determine an average value.

[0083]

[Table 1]

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

[Table 4]

[0087]

According to the present invention, a thermoplastic polymer having good moldability and appearance, and excellent in flexural modulus, tensile elongation characteristics, surface hardness, impact resistance or paintability, and thermoplasticity are provided. The fact that a polymer composition is obtained is as described above in the section "Summary of the Invention".

──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hiroki Sato 1 Toho-cho, Yokkaichi-shi, Mie Prefecture Inside Yokkaichi R & D Co., Ltd. (72) Inventor Hideo Sakurai 1 Toho-cho, Yokkaichi-shi, Mie Prefecture (56) References JP-A-1-193346 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 210/16 C08K 3/34 C08L 23/16

Claims (3)

(57) [Claims] 1. A thermoplastic polymer comprising a step of bringing an olefin into contact with a stereoregular catalyst and polymerizing the same, wherein the polymerization step comprises the following polymerization steps (1) to (4): process (where a range polymerization ratio of 1/2 to 2 with polymer produced by the generated polymer and polymerization process by polymerization step (3) (4), the polymerization step
(1) -Total of polymers produced by polymerization step (4)
Is 100% by weight ). Polymerization Step (1) Homopolymerization of propylene is performed to obtain a density of 0.908 g.
/ Cm ³ or more to produce a homopolymer of propylene (however, the polymerization amount in this step is 50 to 7 of the total polymerization amount)
0% by weight). Polymerization step (2) Ethylene / propylene reaction ratio is 30 / 70-50 / 50
(Weight ratio) by supplying an ethylene / propylene mixture to the polymerization system to form an ethylene-propylene copolymer (however, the polymerization amount in this step is 2 to 10% by weight of the total polymerization amount). Corresponding amount). Polymerization step (3) Ethylene / propylene reaction ratio is 90/10 to 70/30
(Weight ratio) to supply an ethylene / propylene mixture to the polymerization system to produce an ethylene-propylene copolymer (however, the polymerization amount in this step is 8 to 25% by weight of the total polymerization amount). Corresponding amount). Polymerization Step (4) A step of supplying an ethylene / butene mixture to a polymerization system so that an ethylene / butene reaction ratio becomes 90/10 to 70/30 (weight ratio) to form an ethylene-butene copolymer (however, The polymerization amount in this step is an amount corresponding to 8 to 25% by weight of the total polymerization amount). 2. The polymerization steps (1) to (4) are performed in the order of polymerization step (1) -polymerization step (2) -polymerization step (3) -polymerization step (4) or polymerization step (1) -polymerization step. (2)-
The process for producing a thermoplastic polymer according to claim 1, wherein the process is carried out in the order of polymerization step (4) -polymerization step (3). 3. The propylene homopolymer produced in the polymerization step (1) has a pore volume of 0.05 cm ³ / g or more in a pore diameter range of 100 to 2,000 Å. The method for producing a thermoplastic polymer according to claim 1.