JPH0249046A - Polypropylene-based resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition useful for injection molding, suitable as bumper for automobiles, spoilers, helmets for motorcycle, housings for household electric appliances, etc., comprising a PP-based resin and a specific alpha-olefin polymer in a specific ratio. CONSTITUTION:The aimed composition comprising (A) 30-80wt.% PP-based resin (preferably block copolymer of ethylene and propylene) and (B) 20-70wt.% alpha-olefin polymer (preferably polyhexene-1, polyoctene-1 or polydecene-1 having 100,000-400,000 molecular weight) comprising one or more alpha-olefins selected from 6-20C alpha-olefins.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polypropylene resin composition, and more particularly, to a softened polypropylene resin composition that can be used by injection molding to provide industrial products with good performance. The present invention relates to a resin composition.

[Prior Art] Conventionally, ethylene propylene rubber (EPM) is often used to soften polypropylene resins. but,
The current situation is that unless EPM is blended in an amount of 40 to 50 parts by weight per 100 parts by weight of a polypropylene resin composition, a softening composition that can be used for various intended industrial products cannot be obtained.

[Problems to be Solved by the Invention] The present invention is capable of softening polypropylene resin with a relatively small amount of blend compared to the case of EPM.
Another object of the present invention is to provide a softer polypropylene composition even at the same blending ratio as EPM.

[Means for Solving the Problems] In view of the above-mentioned conventional technical problems, the present inventors conducted extensive research on softening polypropylene resins, and found that a) 30 to 80% by weight of polypropylene resins, and b) α-olefin polymer consisting of one or more α-olefins selected from α-olefins having 6 to 20 carbon atoms
It has been discovered that a soft polypropylene resin composition can be obtained by blending 20 to 70% by weight, and the present invention has been achieved.

The present invention will be explained in detail below.

As the polypropylene resin a) used in the present invention, commercially available polypropylene homopolymers, random copolymers of ethylene and propylene, and block copolymers of ethylene and propylene are used, and among these, block copolymers of ethylene and propylene are preferred.

b) an α-olefin composed of one or more α-olefins selected from α-olefins having 6 to 20 carbon atoms used in the present invention;
The constituent components of the olefin polymer include hexene-1,
4-methylpentene-1, heptene-1,4,4-dimethyl-pentene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1
1, tetradecene-1, pentadecene-1, hexadecene-1, pentadecene-1, octadecene-1, nonadecene-1, eicosene-1, and the like.

Although these components can be used in any combination, polyhexene is preferably used as the polymer.
] 1. An α-olefin polymer containing 60 mol% or more of any one of polyoctene-1, polydecene-1, hexene-1, octene-1, and decene-1, and when blended as a composition. may be an α-olefin polymer component obtained by blending these polymers.

The preferred molecular weight of these α-olefin polymers is 10.
000 to 500,000, particularly preferably 100,00
0 to 400.000.

These α-olefin polymers can be produced using a so-called Ziegler-Natta type catalyst.

The transition metal compound components of the Ziegler-Natta type catalyst are:
Among these, titanium compounds and compositions thereof are preferred. Particularly preferable examples of this titanium compound or its composition include titanium tetrachloride, and titanium trichloride compositions (e.g. TiCl3・n A I C13), a titanium trichloride composition obtained by co-pulverizing this titanium trichloride composition with an electron-donating compound such as an organic acid ester, ether, phosphoric acid amide, etc.; A titanium trichloride composition obtained by reduction with aluminum and then ether treatment and Lewis acid treatment, a reaction product of magnesium oxychloride and alkyl aluminum dichloride (a compound obtained by further reacting these with a siloxane compound if desired), Alternatively, using magnesium chloride as a carrier, electron donating compounds (organic acid esters, alcohols, amines, organic acid amides, ethers, water) and halogen-containing titanium compounds (e.g. titanium tetrachloride, titanium trichloride,
These include supported titanium catalyst components containing alkoxy titanium trichloride, etc., as essential components.

As the organometallic compound component, which is another component of the Ziegler-Natta type catalyst, organometallic compounds of groups 1 to 3 of the periodic table are suitable, and among them, organometallic compounds of group 3 metals, particularly aluminum, are preferably used. . Examples of organoaluminum compounds that are usually preferably used include (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and trihexylaluminum;
(b) dialkylaluminum halides such as diethylaluminum chloride, di-n-propylaluminum chloride, and diisobutylaluminum chloride; (c) dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride;
d) Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, n-propylaluminum sesquichloride, and isobutylaluminum sesquichloride; (e) alkylaluminum cybarides such as methylaluminum dichloride, ethylaluminum dichloride, and isopropylaluminum dichloride; , (to) diethylaluminum ethoxide, diethylaluminium isopropoxide, di-n-propylaluminium-2,6-di-t-
These include dialkylaluminum alkoxides or aryloxides such as butyl phenoxide, (t)dimethylaluminum trimethylsiloxide, diethylaluminum trimethylsiloxide, and the like.

Alternatively, these organic aluminum and water or a second
It may also be a reaction product with a class amine or an organic acid ester. Two or more types of these organoaluminum compounds can also be used in combination.

Preferred polymerization conditions for b) the α-olefin polymer used in the present invention include a polymerization temperature of 0 to 200°C, particularly preferably 20 to 150°C, and a polymerization pressure of 0 to 150 kg/cJ.
G, particularly preferably 0 to 50 kg/cd.G1 Polymerization time 0.1 to 10 hours, particularly preferably 0.5 to 2 hours. There are no particular restrictions on the polymerization mode, and (a) n
-hexane, n-hebutane, n-octane, toluene,
A slurry method or a solution method using an inert solvent such as benzene or cyclohexane, and (b) a slurry method or a melt method in which an α-olefin acts as a solvent without substantially adding a solvent are used. Furthermore, hydrogen and/or an alkylzinc compound can be used as a molecular weight regulator for the polymer.

The polypropylene resin composition of the present invention comprises: a) 40 to 80% by weight of polypropylene resin, preferably 30 to 80% by weight of polypropylene resin;
b) 20-60% by weight of α-olefin polymer
, preferably 20 to 70% by weight. a) If the polypropylene resin is less than 30% by weight, the resulting resin composition will not be able to form a pellet shape, which is not preferable. Moreover, if it exceeds 80 degrees, the flexural modulus becomes too high, which is not preferable.

In producing the polypropylene resin composition of the present invention, fillers such as talc, silica, and glass fiber can be used within a range that does not significantly increase the flexural modulus. Further, a heat stabilizer, an ultraviolet absorber, a coloring agent, etc. can also be used as necessary. Furthermore, partial crosslinking can be achieved by treatment with an organic peroxide.

In producing the polypropylene resin composition of the present invention, a Banbury mixer, a kneader blender, an intermixer, a continuous kneader, and an extruder can be used.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, parts and percentages are heavy parts, unless otherwise specified.
Indicates weight %.

In this example, the number average molecular weight of the polymer in terms of polystyrene was measured at 135° with trichlorobenzene solvent using a Waters Model 150 gel perfusion chromatograph.
Measured at C. In addition, the age of hexene-1 in the copolymer in this example is determined by the area of the spectrum determined by the Lindeman and Adams calculation formula using JNM-FX100 type carbon-13NMR (13C-NMR) manufactured by JEOL Ltd. Using an infrared spectrometer needle (IR) model A-302 manufactured by JASCO Corporation, focus on the peaks derived from each component, and use a calibration curve created using known samples made from polymer blends in advance. Ta.

In this example, the bending modulus was measured using JIS K3PO4.
The Izot impact strength was determined according to JIS K7.
110 (with V-notch). Furthermore, Table 1
NB in the middle means non-break (not broken).

Example-1 A. Production of α-olefin polymer In a 5ρ flask that had been purged with nitrogen in advance, 3 g of dehydrated and purified n-hexane and 300 g of dehydrated and purified hexene-1 (Dialene-6, manufactured by Mitsubishi Kasei Corporation) were charged. Next, 15 mmol of triisobutylaluminum and 0.3 mmol of supported Ti catalyst (prepared according to Example 1 of JP-A-63-223010) were charged, and the mixture was stirred at 30°C for 1 hour.

Thereafter, 10 ml of isopropyl alcohol was added to stop the polymerization reaction, and the polymerization reaction solution was blown with steel to remove the solvent, and dried with a roll at 100°C.

The total yield of the polymer was 140 g, and the number average molecular weight in terms of polystyrene was 119,000 (this polymer was
(referred to as X).

Measurement of physical properties of B1 composition Using PHX and Mitsubishi Noblen BC-2 (polypropylene resin, manufactured by Mitsubishi Yuka Co., Ltd.), 15% was measured in a 250cc blast mill (manufactured by Toyo Seiki Co., Ltd.) according to the formulation shown in Table 1.
After kneading at 0°C for 110 minutes, the mixture was sheeted using cold rolls. The obtained sheet was formed into a square pellet, a sample piece was prepared by injection molding, and the physical properties were measured.

The results are shown in Table-1.

The composition of this example exhibits a low bending modulus, indicating that it is a good soft material.

Comparative Example-1 Physical Properties of B0 Composition In Example-IB, JSREP0 was used instead of PHX.
The physical properties were measured in the same manner as in Example-1 except that 2P (EPM, manufactured by Japan Synthetic Rubber Co., Ltd.) was used. The results are shown in Table-1. It can be seen that when EPM is used instead of PHX, the bending modulus is about 50% higher, which is not preferable.

Example-2 A, α ~ Production of olefin polymer Example-IA except that 1195 ml of hexene and 95 ml of decene-1 (Dialene 10, manufactured by Mitsubishi Kasei Corporation) were used instead of 1300 ml of hexene. −
Polymerization was performed in the same manner as IA.

The yield of the polymer was 151 g, and the number average molecular weight in terms of polystyrene was 127,000.13 cm.
1 content was 63 mol% (this polymer is referred to as PHD).

Physical Properties of B0 Composition In Example-1B, physical properties were measured in the same manner as in Example-IB except that PHD was used instead of PHX. The results are shown in Table-1.

As in Example-1, it was found to be a good soft material.

Examples-3, 4 and Comparative Examples-2 to 4 Physical Properties of B1 Composition In Example-IB, physical properties were measured in the same manner as in Example-IB, except that each component was used in the proportions shown in Table-1. .

The results are shown in Table-1.

Examples 3 and 4 exhibited lower flexural modulus than Comparative Example 2, and were good.

Example-5 A, Production of α-olefin polymer In Example-IA, hexene-1270mL 4-methylpentene-13 was used instead of hexene-1300ml.
Polymerization was carried out in the same manner as in Example-IA except that 0ml (manufactured by Mitsubishi Yuka Co., Ltd.) was used.

The yield of the polymer was 138 g, the number average molecular weight in terms of polystyrene was 115,000, and the hexene-1 content by IR method (measured with an infrared spectrophotometer) was 87 mol% (this polymer is referred to as P HMP). ).

Physical Properties of B9 Composition In Example-IB, physical properties were measured in the same manner as in Example-IB except that P)1MP was used instead of PHX. The results are shown in Table-1.

Similar to Example-1, this example was also found to have a good soft phase.

[Effects of the Invention] According to the present invention, a good soft polypropylene resin composition can be obtained, which is useful for various industrial products such as automobile bumpers, spoilers, motorcycle helmets, and housings for home appliances.

Patent applicant: Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Scope of Claims] 1) α-olefin polymer consisting of a) 30 to 80% by weight of a polypropylene resin, and b) one or more α-olefins selected from α-olefins having 6 to 20 carbon atoms 20 A polypropylene resin composition consisting of ~70% by weight.