JP3323016B2 - Polypropylene composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to polypropylene compositions. More specifically, the present invention relates to a polypropylene composition comprising a specific propylene polymer and an α-olefin elastomer.

[0002]

2. Description of the Related Art Polypropylene is widely used because it is inexpensive, has excellent mechanical performance balance, and has good solvent resistance and heat resistance. Thermoplastic elastomers have excellent electrical, mechanical and chemical properties and can be obtained at a low cost, so they are very well used as an improver for polypropylene molding processability and a balance of physical properties. Have been. Recently, a method has been known in which these thermoplastic elastomers are added to a propylene / ethylene block copolymer in order to improve the impact resistance of polypropylene.

However, when these thermoplastic elastomers are used as a physical property modifier for polypropylene, the effect of improving the impact resistance is great, but the heat resistance and rigidity are reduced, so that the amount of addition is limited, and the rigidity of the molded product is reduced. When evaluated as a balance of impact resistance, there is a problem that the balance itself hardly changes. In order to solve this problem, to improve the physical properties of conventional polypropylene, the stereoregularity of the polypropylene homo part was increased to change the molecular weight distribution, or a method of mixing polypropylene having different physical properties or adding various nucleating agents, etc. It is generally known to improve rigidity and impact by adding various rubbers having different properties to improve the balance between rigidity and impact resistance.

[0004]

However, in the conventional method, the rubber is added to improve the impact resistance.
Impact resistance can be improved due to the addition of soft rubber, but rigidity is reduced, and means of increasing rigidity, such as increasing the tacticity to change the molecular weight distribution or adding nucleating agents in combination, use polypropylene. Although the crystallinity of the compound increases and the rigidity increases, the impact resistance decreases. Thus, there is a problem that the balance of physical properties is not always satisfactory, and it is easy to improve either the rigidity or the impact resistance, but it is difficult to improve it in a well-balanced manner. It has been desired to develop a compound useful for improving the balance between rigidity and impact resistance.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems and completed the present invention. That is, the present invention relates to (1) a silane compound having at least two or more Si-H bonds in a mixture of a propylene polymer (A) having a terminal unsaturated bond and an α-olefin elastomer (B) having an unsaturated bond. (2) a propylene-based resin obtained by subjecting C) to an addition reaction in the presence of a catalyst and having a boiling para-xylene-insoluble content of 10% by weight or less and a melt flow rate in the range of 0.1 to 1000 g / 10 minutes; It is a polypropylene composition obtained by mixing with crystalline polypropylene.

The propylene polymer having a terminal unsaturated bond used in the present invention may be not only a propylene homopolymer but also a random copolymer or a block copolymer containing 20 mol% or less of ethylene or butene. A propylene polymer having such a terminal unsaturated bond is, for example, propylene and α having an unsaturated bond at both terminals.
It can be obtained by copolymerizing -ω diene or the like. Such olefin polymerization can be produced by a bulk polymerization method or a gas phase polymerization method in addition to a solvent method using an inert solvent. Further, a catalyst comprising a transition metal compound and an organometallic compound is generally used as a catalyst used in the production. A titanium halide is preferably used as the transition metal compound, and an organoaluminum compound is preferably used as the organometallic compound.

Specifically, titanium tetrachloride obtained by reducing titanium tetrachloride with metallic aluminum, hydrogen or organic aluminum is modified with an electron donating compound, an organic aluminum compound, and if necessary, an oxygen-containing organic compound. A catalyst system comprising an electron donating compound such as, or a carrier such as magnesium halide or a transition metal compound catalyst obtained by supporting them with an electron donating compound and supporting a titanium halide, and an organoaluminum compound. A catalyst system consisting of an electron donating compound such as an oxygen-containing organic compound, or a reaction product of magnesium chloride and an alcohol is dissolved in a hydrocarbon solvent, and then treated with a precipitant such as titanium tetrachloride to form a hydrocarbon solvent. Insolubilize and treat with an electron-donating compound such as an ester or ether if necessary. A catalyst system comprising a transition metal compound catalyst and an organoaluminum compound obtained by a method of treating with a titanium logenide and an electron-donating compound such as an oxygen-containing organic compound as necessary, or a Grignard reagent or a magnesium alkoxide in a hydrocarbon solvent. , And then precipitated by reacting with a halogenating agent such as silicon tetrachloride to make it insoluble in a hydrocarbon solvent, and if necessary, treating with an electron-donating compound such as an ester or ether. Examples of the catalyst system include a transition metal compound catalyst obtained by the method of treating with an organic compound and an organoaluminum compound, and, if necessary, an electron-donating compound such as an oxygen-containing organic compound.

Here, as the electron donating compound, oxygen-containing compounds such as ether, ester, orthoester and alkoxysilicon compound can be preferably exemplified, and alcohol, aldehyde, water and the like can also be used.

As the organoaluminum compound, trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide can be used. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Illustrative examples of the halide include chlorine, bromine and iodine.

A metallocene compound belonging to Group 3, 4 or 5 of the periodic table having an unsaturated hydrocarbon compound such as a cyclopentadienyl derivative as a ligand, and, if necessary, an organic aluminum and water or water of crystallization Activator comprising an aluminoxane compound which is an oligomer or polymer obtained by reacting the above, or a metal cation complex of Group 3, 4 or 5 of the periodic table having a cyclopentadienyl compound as a ligand Some propylene polymers polymerized using a catalyst that combines an activator consisting of a compound that forms a stable anion with the one that contains a terminal unsaturated bond, so these propylene polymers are used as they are. You can also.

The molecular weight of the polymer is not particularly limited, but the molecular weight is preferably as high as possible from the viewpoint of the physical properties of the molded product. In terms of moldability, if the molecular weight is too high, moldability deteriorates.
The intrinsic viscosity measured with a tetralin solution of 0.5 to 10 d
It is about 1 / g, particularly preferably about 0.8 to 5.0 dl / g.

The α-ω diene having an unsaturated bond at both terminals used for synthesizing the propylene polymer having a terminal unsaturated bond of the present invention has at least a vinyl group at the α-position, and has a vinyl group at the ω-position. Any diene compound having an unsaturated bond may be used, which may be linear or branched, and oxygen, sulfur,
It may contain a hetero atom or an atomic group such as boron. For example, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1 , 11-
Dodecadiene, 1,13-tetradecadiene, 5-methyl-1,5
-Hexadiene, 6-methyl-1,6-heptadiene, 7-methyl-1,7-octadiene, 8-methyl-1,8-nonadiene, 9-
Examples thereof include methyl-1,9-decadiene, 10-methyl-1,10-undecadiene, divinylbenzene and the like.

The number of terminal unsaturated bonds contained in these propylene polymers having terminal unsaturated bonds is not particularly limited. However, in order to increase the reactivity, a polymer having an average of 0.1 or more per molecular chain is required. It is preferable to use coalescence,
If the number of terminal unsaturated bonds is less than this, the reaction may be difficult to occur.

The upper limit of the number of terminal unsaturated bonds contained in the propylene polymer having terminal unsaturated bonds is not particularly limited, but the number of terminal unsaturated bonds per 1,000 carbon atoms in the molecule is more than 1. Depending on the reaction conditions and the like, the molecular weight of the obtained composition becomes very large, the polymer becomes insoluble in the solvent, and the infused portion becomes present even when heated, and the moldability deteriorates and the physical properties deteriorate. Therefore, it is preferable to control the reaction by reducing the amount of the catalyst or the ratio of the silane compound having at least two or more Si—H bonds.

As the α-olefin elastomer having an unsaturated bond used in the present invention, a propylene / ethylene / diene copolymer elastomer or the like is industrially available. It can also be obtained by copolymerizing an α-ω diene having an unsaturated bond. In addition, a propylene / ethylene elastomer produced using a catalyst containing the above-mentioned metallocene compound as a main component, propylene or ethylene and α-
Since an unsaturated bond is contained in the copolymer elastomer with olefin, these α-olefin elastomers can be used as they are.

The number of unsaturated bonds contained in the α-olefin elastomer having an unsaturated bond is not particularly limited. However, like the above-mentioned propylene polymer having a terminal unsaturated bond, it is necessary to increase the reactivity. It is preferable to use a polymer having an average of 0.1 or more per one molecular chain, and if the number of unsaturated bonds is smaller than this, the reaction may be difficult to occur. Α having an unsaturated bond
-The upper limit of the number of unsaturated bonds contained in the olefin elastomer is not particularly limited, but 1000 carbon atoms in the molecule.
If the number of unsaturated bonds per unit is more than 1, the molecular weight of the copolymer becomes extremely large depending on the reaction conditions, etc., so that the polymer becomes insoluble in the solvent, and the infusible portion exists even when heated. The reaction is controlled by reducing the amount of the catalyst and the ratio of the silane compound having at least two or more Si-H bonds, since the molding processability is deteriorated and the physical properties are deteriorated, thereby deteriorating the industrial utility value. There is a need to.

In the present invention, at least two or more Si
Examples of the silane compound having an -H bond include compounds represented by the following general formulas (Chem. 1), (Chem. 2), (Chem. 3), and (Chem. 4).

[0018]

Embedded image R _n SiH _4-n (where n is 0 to 2 and R is a hydrocarbon residue having 1 to 12 carbon atoms)

[0019]

Embedded image R ₃ Si— (X) _n —SiR ₃ (wherein R represents hydrogen and a hydrocarbon residue having 1 to 12 carbon atoms, at least two of which are hydrogen. X represents a hydrocarbon residue. Or a —SiR ₂ — group.)

[0020]

Embedded image R ₃ Si—O — (— SiR ₂ —O—) _n —SiR ₃ (wherein n is an integer of 0 or more, R is hydrogen, a hydrocarbon residue having 1 to 12 carbon atoms, and At least two are hydrogen.)

[0021]

Embedded image (In the formula, n is an integer of 3 or more, R is hydrogen, a hydrocarbon residue having 1 to 12 carbon atoms, and at least two of them are hydrogen.)

More specifically, silane, methylsilane, dimethylsilane, ethylsilane, diethylsilane, phenylsilane, diphenylsilane, propylsilane, dipropylsilane, butylsilane, dibutylsilane, hexylsilane, dihexylsilane, methylethylsilane, methylpropylsilane , Isopropylsilane, diisopropylsilane, methylphenylsilane, ethylphenylsilane,
Cyclohexylmethylsilane, dicyclohexylsilane, allylsilane, butenylsilane, pentenylsilane, dimethoxysilane, dichlorosilane, diethoxysilane, and other monosilane compounds and disilanes, dimethyldisilane, diethyldisilane, methylphenyldisilane, diphenyldisilane, dipropyldisilane, dihexyldisilane , Polysilane compounds such as trisilane, trimethyltrisilane, triphenyltrisilane, tetrasilane, and dimethyltetrasilane, and cyclic polysilane compounds in which these are cyclic, dimethyldisiloxane, diethyldisiloxane, diphenyldisiloxane, dibutyldisiloxane, and dimethoxydisiloxane. Siloxane compounds such as siloxane and diethoxydisiloxane and cyclic polysiloxanes in which these are cyclic Such compounds or mixtures thereof can be exemplified.

In the present invention, in the reaction, a propylene polymer having a terminal unsaturated bond and an α-olefin elastomer having an unsaturated bond are used to determine the number of terminal unsaturated bonds contained in the propylene polymer having a terminal unsaturated bond. It is preferable to use each of them in such a ratio that the value divided by the number of unsaturated bonds contained in the α-olefin elastomer having an unsaturated bond is in the range of 0.1 to 10. Outside this range, the reaction between the propylene polymer having a terminal unsaturated bond and the α-olefin elastomer having an unsaturated bond hardly occurs, and the effect of improving the rigidity and impact resistance in a well-balanced manner is reduced. is there.

In the present invention, at least two Si
The use ratio of the silane compound having a -H bond to the propylene polymer having a terminal unsaturated bond varies depending on reaction conditions and a desired degree of reaction, and is usually based on 100 parts by weight of the propylene polymer having a terminal unsaturated bond. 0.
It is from 0.1 to 10 parts by weight, preferably from 0.1 to 5 parts by weight. If the amount is less than the above, crosslinking hardly occurs, and if the amount is too large, the propylene-based resin may be gelled, and the insoluble matter in the boiling paraxylene increases.

The reaction method for adding a silane compound having at least two or more Si—H bonds to the propylene polymer having a terminal unsaturated bond is not particularly limited, and the terminal unsaturation is carried out in the usual manner in the presence of a catalyst. The propylene polymer having a bond can be dissolved in a solvent or mixed with a catalyst in a powder state, and then melt-kneaded and reacted. The reaction temperature is from room temperature to 150 ° C. when a solvent is used, and 150 ° C. to 300 ° C. when the reaction is performed by melt kneading.

In the present invention, as the catalyst, a compound generally known as a hydrosilylation catalyst can be used. For example, chloroplatinic acid, chloroplatinic acid, bromoplatinic acid, platinum salts such as benzonitrile complexes and alkoxy complexes of platinum chloride, acetonitrile complexes and alkoxy complexes of palladium chloride, palladium salts such as cyclooctadiene complexes, and chlorides Rhodium salts such as rhodium cyclooctadiene complex and triphenylphosphine complex; metallocene compounds such as titanocene dichloride, zirconocene dichloride and hafnocene dichloride; and titanates and the like represented by the following general formula (Formula 5) Preferable examples include compounds of Group 4 metals.

[0027]

Embedded image _{^{R 1 n M (O-R}} 2) 4-n ( wherein R ^1, R ² is a hydrocarbon residue of the same or different carbon atoms 1 to 12, n is an integer of 0 to 4, M is A metal selected from titanium, zirconium and hafnium is shown.) A radical generator such as a peroxide can also be used.

The catalyst is contacted by dissolving a silane compound having at least two or more Si-H bonds in a solvent in a mixture of a propylene polymer having a terminal unsaturated bond and an α-olefin elastomer having an unsaturated bond. When mixing or heating and melting, the amount of the catalyst used is 0.1 to 100 with respect to the entire polymer.
000 ppm, preferably 1-10000 ppm.

As the solvent used here, specifically, a hydrocarbon compound having 1 to 20 carbon atoms and a halogenated hydrocarbon compound can be used, and a halogenated hydrocarbon compound and an aromatic hydrocarbon compound are particularly preferably used. Is done. Specific examples include hexane, heptane, cyclohexane, benzene, toluene, xylene, ethylbenzene, dichloromethane, chloroform, dichloroethane, trichloroethane, perchloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene and the like.
It is used after being dissolved so as to have a catalyst concentration of 10,000 ppm.

In the case where the catalyst is brought into contact with the mixture by heating and melting without using a solvent, there is no particular limitation on the method of mixing the above-mentioned components and the method of mixing with the additives. , A V-type blender or the like, and then melt-mixed for 30 seconds to 10 minutes with an extruder or a roll, a Banbury mixer, a kneader or the like.

The propylene-based resin thus obtained in the present invention preferably has a melt flow rate in the range of 0.1 to 1000/10 minutes. When the melt flow rate is out of this range, the moldability deteriorates, which is not preferable. The molecular weight is 135
0.1 ~ the intrinsic viscosity measured in tetralin solution at
About 10 dl / g is preferable.

The propylene resin of the present invention is characterized in that the boiling para-xylene insoluble content is 10% by weight or less. Those having a boiling para-xylene insoluble content of more than 10% by weight are not preferred because not only the appearance of the molded product becomes poor, but also the gel is present in the molded product, and as a result, the effect of improving the physical properties is lost.

The crystalline polypropylene used in the present invention includes not only propylene homopolymer but also
Examples thereof include a random copolymer of propylene and ethylene having crystallinity, or a propylene / ethylene block copolymer. These polypropylenes are industrially produced, and they can be obtained and used, or can be produced using a catalyst for polymerizing the above-mentioned propylene polymer having a terminal unsaturated bond.

The method for producing the polypropylene composition of the present invention is not particularly limited, and a compound obtained by reacting a propylene polymer having a terminal unsaturated bond with an α-olefin elastomer having an unsaturated bond is mixed with crystalline polypropylene. There is no particular limitation on the mixing method,
A method of mixing in a solution or a method of melting and mixing are exemplified.

In obtaining the propylene-based resin or polypropylene composition of the present invention, antioxidants, ultraviolet absorbers, lubricants,
Addition of various known stabilizers such as antistatic agents or other nucleating agents, as well as various inorganic and organic fine particles, for example, silica, alumina, kaolin, talc, zeolite,
Titanium oxide, calcium carbonate, calcium silicate, stearic acid ester and the like can be added and used.

[0036]

The present invention will be further described with reference to the following examples.

Example 1 [Synthesis of propylene polymer having terminal unsaturated bond]
Into a stainless steel autoclave having an internal volume of 3000 liters, 140 liters of toluene was added, and methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd., polymerization degree 16.2) 12
0 g and 341 g of 1,5-hexadiene were charged. Further, propylene gas is introduced at 20 ° C. and 3 kg / cm ² −
As G, a solution prepared by dissolving 420 mg of dimethylsilylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride synthesized in a conventional manner in 3 liters of toluene was added, and polymerized at 20 ° C. for 2 hours. After completion of the polymerization, unreacted propylene was purged, the polymer was filtered out, vacuum-dried at 80 ° C. for 8 hours, and weighed to obtain 16.7 kg of a propylene polymer. The composition of the reaction solution before and after the polymerization was analyzed by gas chromatography, and 1,5-
The calculated reaction amount of hexadiene was 251 g.

The resulting infrared absorption spectrum of the propylene polymer has absorbed vinyl groups 906cm ^-1 and 1640 cm ^-1, The absorption of vinylidene group in the 884cm ^-1 was observed, calculated from ¹ H-NMR The number of the terminal unsaturated bonds was 20 mmol per 100 g of the polymer. The mmmm pentad fraction determined from ¹³ C-NMR was 0.98, and the intrinsic viscosity (hereinafter referred to as [η]) measured with a tetralin solution at 135 ° C. was 1.48 dl /.
g, the ratio of the weight average molecular weight to the number average molecular weight (hereinafter referred to as Mw / Mn) measured by gel permeation chromatography using 1,2,4-trichlorobenzene was 4.6.

[Addition reaction of silane compound] 3 kg of the above propylene polymer, 300 g of propylene / ethylene / diene elastomer (EPDM, JSR-EP24, manufactured by Nippon Synthetic Rubber Co., Ltd., iodine value 15), 50 g of tetramethyldisilane, and chloride 1 g of a rhodium triphenylphosphine complex is added together with 0.1 parts by weight of an antioxidant, and the mixture is heated and mixed at 230 ° C. with an extruder to produce a propylene-based resin (pellet)
I got The obtained propylene-based resin is soluble in boiling para-xylene and has a melt flow rate of 25.2 g / 10
Minutes.

For 10 parts by weight of this propylene-based resin,
Polypropylene sold by Mitsui Toatsu Chemicals, Inc.
Blen J3H-G) Injection molding machine by mixing 90 parts by weight
(FKS55T, manufactured by Komatsu Ltd.)
A test piece for measuring physical properties was prepared and the physical properties were measured.
The physical properties were measured according to the following methods. -Flexural modulus: ASTM-D790-Flexural strength: ASTM-D790-Tensile strength: ASTM-D638-Tensile elongation: ASTM-D638-Izod impact strength: ASTM-D256 (with notch)
23 ° C., −10 ° C.) As a result, the flexural modulus was 198.
00kg / cm^Two, Bending strength is 565kg / cm ^Two, Pull
Tensile strength is 405kg / cm^Two, Extension 508kg
/ Cm^Two, Izod impact strength (23 ℃, -10 ℃)
The values were 7.1 and 2.3 kg · cm / cm, respectively.

Comparative Example 1 The physical properties were measured in the same manner as in Example 1 except that the propylene resin obtained by the addition reaction with the silane compound was not added. As a result, the flexural modulus was 16,400 kg / cm ² and the flexural strength was 484 kg / cm ² , tensile strength 388 kg / cm
² , tensile elongation 583 kg / cm ² , Izod impact strength (23 ° C., -10 ° C.) 2.4, 1.6 kg, respectively
Cm / cm.

Example 2 [Synthesis of propylene polymer having terminal unsaturated bond]
Polymerization was carried out in the same manner as in Example 1 except that 227 g of 1,7-octadiene was used instead of 1,5-hexadiene to obtain 18.6 kg of a propylene polymer. The composition of the reaction solution before and after the polymerization was analyzed by gas chromatography, and the reaction amount of 1,7-octadiene was calculated to be 186 g.

The resulting infrared absorption spectrum of the propylene polymer has absorbed vinyl groups 906cm ^-1 and 1640 cm ^-1, The absorption of vinylidene group in the 884cm ^-1 was observed, calculated from ¹ H-NMR The number of terminal unsaturated bonds was 10 mmol per 100 g of the polymer. The mmmm pentad fraction determined from ¹³ C-NMR was 0.98, [η] was 1.36 dl / g, and Mw
/ Mn was 3.6.

[Synthesis of α-olefin elastomer having unsaturated bond] 227 g of 1,7-octadiene, 15.75 kg of ethylene and 23.75 kg of propylene were charged and polymerized at 20 ° C. for 1 hour. After the polymerization was completed, unreacted ethylene and propylene were purged, a large amount of methanol was added to precipitate a polymer, and the polymer was filtered out. The polymer was vacuum-dried at 80 ° C. for 8 hours and weighed.
8 kg of a propylene / ethylene / 1,7-octadiene elastomer were obtained.

From the infrared absorption spectrum, ethylene was 52%
Was included. 906 cm ^-1 and 1640 cm
^-1 showed absorption of a vinyl group, and 884 cm ^-1 showed absorption of a vinylidene group. ^{In 1} H-NMR, a signal of a terminal vinyl group was observed at around 6 ppm, and the amount was 10 mmol per 100 g of the polymer. Also,
[Η] was 1.21 dl / g, and MW / MN was 3.1.

[Addition reaction of silane compound] 1.5 kg of a propylene polymer having an unsaturated bond at the terminal, 1.5 kg of a propylene / ethylene / diene elastomer and methyl hydrogen silicone (TSF manufactured by Toshiba Silicone Co., Ltd.)
484) 100 g and 1.5 g of a triphenylphosphine complex of rhodium chloride were added together with 0.1 part by weight of an antioxidant, and the mixture was heated and mixed at 230 ° C. with an extruder to obtain a propylene-based resin (pellet). The obtained propylene-based resin is soluble in boiling para-xylene and has a melt flow rate of 1.
It was 2 g / 10 minutes.

Example 1 was repeated except that 95 parts by weight of a commercially available polypropylene (Mitsui Noblen, BJHH-G, manufactured by Mitsui Toatsu Chemicals, Inc.) was used for 5 parts by weight of the propylene resin.
As a result of mixing, a test piece for measuring physical properties was prepared and the physical properties were measured. As a result, the flexural modulus was 12800 kg / cm.
² 、 Bending strength is 380kg / cm ² , Tensile strength is 31
7 kg / cm ^2, tensile elongation 819kg / cm ^2, an Izod impact strength (23 ℃, -10 ℃), respectively 14.
6, 9.6 kg · cm / cm.

Comparative Example 2 The physical properties were measured in the same manner as in Example 2 except that the propylene resin obtained by the addition reaction with the silane compound was not added. As a result, the flexural modulus was 11,100 kg / cm ² and the flexural strength was 355 kg / cm ² , tensile strength is 293 kg / cm
² , tensile elongation 871 kg / cm ² , Izod impact strength (23 ° C., −10 ° C.) 9.3 and 4.0 kg, respectively
Cm / cm.

Example 3 [Synthesis of propylene polymer having terminal unsaturated bond]
A solution of 5.7 g of triisobutylaluminum and 20 mg of dimethylsilylene-bis (2,4-cyclopentadienyl) zirconium dichloride in 200 ml of toluene was placed in a 70-liter autoclave, and 15 kg of liquefied propylene was charged. Then, a solution prepared by dissolving 46 mg of tris (pentafluorophenyl) boron in 50 ml of toluene was added thereto, and polymerized at 60 ° C. for 1 hour. Next, unreacted propylene was purged to take out the polymer, which was dried and weighed to obtain 6.5 kg of a polymer. [Η] of this polymer is 0.45 dl / g, MW /
MN was 2.6. 884 in the infrared absorption spectrum
The absorption of a vinylidene group was observed at cm ^-1 . ¹ H-NMR
In the above, the signal of the terminal vinyl group was observed at around 6 ppm, and the amount was 12 mmol per 100 g of the polymer.

[Addition reaction of silane compound] 1.5 kg of the above-mentioned propylene polymer having a terminal unsaturated bond, 1.5 kg of the propylene / ethylene / diene elastomer used in Example 2, and methyl hydrogen silicone (Toshiba Silicone Co., Ltd.) 100 g of TSF484 (trade name) and 1.5 g of lupazole as a catalyst were added together with 0.1 part by weight of an antioxidant, and heated and mixed at 210 ° C. with an extruder to obtain a propylene-based resin (pellet). The obtained propylene resin is soluble in boiling para-xylene and has a melt flow rate of 14 g / 10
Minutes.

Example 1 except that 95 parts by weight of a commercially available polypropylene (Mitsui Nobren BJHH-G, manufactured by Mitsui Toatsu Chemicals, Inc.) was used for 5 parts by weight of the propylene resin.
As a result of measuring physical properties in the same manner as in the above, the flexural modulus was 127
00 kg / cm ² , flexural strength 375 kg / cm ² , tensile strength 313 kg / cm ² , tensile elongation 835 kg
/ Cm ² and Izod impact strength (23 ° C., −10 ° C.) were 14.1 and 9.9 kg · cm / cm, respectively.

[0052]

Industrial Applicability The polypropylene composition of the present invention is excellent as a compound useful for improving the balance between rigidity and impact resistance of polypropylene, and is extremely valuable industrially.

Claims (1)

(57) [Claims] (1) A silane compound having at least two Si-H bonds is added to a mixture of a propylene polymer having a terminal unsaturated bond and an α-olefin elastomer having an unsaturated bond in the presence of a catalyst. A mixture of a propylene resin having a boiling para-xylene insoluble content of 10% by weight or less and a melt flow rate in the range of 0.1 to 1000 g / 10 minutes and (2) crystalline polypropylene obtained by the reaction. Polypropylene composition.