JPH0328213A - Polyolefin block copolymer composition and its preparation - Google Patents

Abstract

PURPOSE:To prepare a polyolefin block copolymer compsn. with an improved heat resistance and rigidity by polymerizing 3-methylbutene-1 and then polymerizing a monomer component mainly comprising a lower alpha-olefin except 3- methylbutene-1. CONSTITUTION:In the first polymn. step, a monomer component mainly comprising 3-methylbutene-1 is polymerized to produce a crystalline polymer of which 80wt.% of repeating units is 3-methylbutene-1. In the second polymn. step soon after the first step, a monomer component mainly comprising a 2-10C alpha-olefin except 3-methylbutene-1 is polymerized in the presence of the polymer produced in the first step. Thus is prepd. a polyolefin block copolymer compsn. wherein at least a part of the 3-methylbutene-1 polymer is grafted onto a part of the polymer produced in the second step, the wt. ratio of the former polymer to the latter is (90:10)-(10:90), and the melt index is 0.001-1000g/10min.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyolefin block copolymer composition and a method for producing the same.

More specifically, a monomer mainly composed of 3-methylbutene-1 and a carbon number 2-/θ excluding 3-methylbutene-1
The present invention relates to a polyolefin block copolymer composition obtained from monomers containing α-olefin as a main component, and a method for producing the same.

[Conventional technology]

Tokukai Akira! ! -/6! '? In the θt publication, propylene and 3
Random copolymers of -methylphthene/, phlopylene and -methylbentene/, etc. are described. However, the above copolymers cannot be said to have sufficient heat resistance and rigidity.

[Problems to be solved by the present invention]

The present inventors have arrived at the present invention as a result of intensive studies aimed at improving the heat resistance and rigidity of the conventional polyolefin copolymers mentioned above. It wasn't.

[Means for solving problems]

That is, the gist of the present invention is to provide a crystalline polymer component (A) consisting of repeating units containing 1rOwt4 or more of 3-methylbutene units and 90wt% of α-olefin units having 2 to 10 carbon atoms excluding 3-methylphthene units. A composition containing a crystalline polymer component (B) consisting of repeating units containing at least the above polymer component (A).
) and a part of the polymer component (B) constitute a block copolymer, and the polymerization ratio of the polymer component (A) to the polymer component (B) contained in the composition is is in the range of 90:10 to 10:ta0, and the melt index measured at 320°C is in the range of 0.00/~1000ff/10 minutes, and a method for producing the same. .

The present invention will be explained in detail below.

The crystalline polymer component (A) that constitutes the polyolefin composition of the present invention is fOwt%
As mentioned above, the 3-methylbutene-1 homopolymer component 1 or copolymer component preferably contains 90 wt% or more.

In the case of a copolymer component, the comonomer has 2 to 2 carbon atoms.
Examples include 2θ α-olefins. Specifically, ethylene, fluoropylene, phthene/hexene/l. ←Methylpentene/, 3-methylbentene/, octene/
, decene-11, dodecene-11, tetradecene-1, octadecene-1, and the like. Among these, α-olefins having carbon λ~/O are preferable, especially polymer components (B
) is preferably the same as the main component monomer.

A general random copolymerization method is employed as the copolymerization method, but it is more preferable to feed the comonomer intermittently to increase the difference in comonomer concentration and expand the composition distribution of the copolymer.

Furthermore, the polymer component (A) has a main melting peak of 2j as determined by differential scanning calorimetry (DSC).
0°C or higher, preferably 210°C or higher, more preferably 3
Exists at temperatures above 00°C.

The crystalline polymer component (B) constituting the polyolefin composition of the present invention has a carbon number of λ to 1, excluding 3-methylbutene-1.
90 wt% or more of one monomer selected from 10 α-olefins, preferably 5' j wt%
It is a homopolymer component or a copolymer component containing the above.

Here, carbon λ to α of 10 excluding 3-methylphthene/
-Olefins include ethylene, brobylene, butene-/, 4(monomethylbentene-l13-methylpentene-l), etc. Among them, brobylene is particularly preferred.

When the polymer component (B) is a copolymer component, examples of the comonomer include α-olefins having 2 to 20 carbon atoms. Specifically, ethylene, propylene, butene-11
Examples include pentene-/, J-71 tilbutene-l1 hexene-l, goomethylbentene-/, J-methylbentene-l1 octene-l1 decene-l1, dodecene-l1 tetradecene-l1 octadecene-l, and the like.

Particularly preferred polymer component (B) is one consisting of 90 wt% or more of propylene units.

This constitutes the polyolefin block copolymer composition of the present invention. Polymer component (B) with the above polymer component (A)
The composition ratio is in the range of 2θ:10 to 10:90 in polymerization ratio, more preferably 0:2θ to /! vs 1j
It is necessary that A is within the range of (b) and that at least 1 part of the polymer component (A) and 1 part of the polymer (B) constitute a block copolymer. When the ratio b of the polymer component (A) is less than /Owt%, the effect of improving heat resistance and rigidity is small, and when the ratio of the polymer component (B) in the casing is less than 1Owt%, the toughness, especially the impact resistance, decreases. Good! It's not right. At the same time, one part of polymer component (A) and one part of polymer component (B)
The polyolefin block copolymer composition of the present invention has a melt index of 0.5% as measured at 320°C.
00/-10009710 minutes, preferably O. The range is θ/~yoo o y7io minutes, more preferably the range from 0.0~300f//10 minutes.

If the melt index is too small, the moldability will be poor, and if the melt index is too large, the mechanical strength will decrease, which is not preferable.

Examples of the method for producing the polyolefin block copolymer composition of the present invention include the following method.

That is, in the polyolefin block copolymer composition of the present invention, the above polymer component (A) is preferably polymerized from a monomer containing 3-methylbutene-1 as a main component in the presence of a coordination polymerization catalyst. Step and 3-methylbutene-1
A step of polymerizing the above polymer component (B) from a monomer mainly composed of α-olefin having 2 to /θ carbon atoms excluding
It is obtained by multistage polymerization including λ polymerization steps.

Specifically, this polymerization process is carried out using a coordination polymerization catalyst in a liquid olefin, in an aliphatic, alicyclic, or aromatic hydrocarbon such as butane, hexane, hebutane, cyclohexane, benzene, etc., in a liquid olefin. and in the presence of organoaluminum as a cocatalyst. Although either of the above two polymerization steps may be carried out first, a particularly preferred method of the present invention is to carry out 3-
The above polymer component (A) is polymerized from a monomer containing methylbutene/ as a main component, and then immediately subjected to a second polymerization step to obtain a monomer having 2 to 10 carbon atoms excluding 3-meth/l/7'ten-l. The method is characterized in that the above polymer component (B) is polymerized from a monomer whose main component is α-olefin.

In particular, using 3-methylbutene/ as the polymerization solvent, the first
The polymerization step of polymer component (A), which is the polymerization step of 8.
Is it possible to switch between the polymerization process of I2 and the polymerization process of polymer component (B) as quickly as possible? It is preferable to do so.

The above-mentioned method can also be carried out by adding a further polymerization step and carrying out multi-stage polymerization of three or more stages.

Regardless of the manufacturing method. The composition of the resulting polyolefin block copolymer composition is the polymer component (A)
Polymerization is carried out so that the weight ratio of component (B) to polymer component is in the range of 90:10 to /O:90.

The transition metal compound serving as the coordination polymerization catalyst and the organic aluminum compound serving as the cocatalyst are not particularly limited, and those commonly used in the polymerization of olefins can be used. Preferably, it is a combination of a solid catalyst component containing Mg%Ti1 halogen and an electron-donating compound such as an ether or ester, an organoaluminum compound, and, if necessary, an electron-donating compound such as an ether or ester. Such a solid catalyst component is described in Japanese Patent Application Laid-Open No. 1071-1071.
Same as Publication No. 3-2'l371, same! r3-43177 publication, r3-//7013 publication, r3-43177 publication, r3-//7013 publication, same! Tar 42 0
It is described in Publication No. V, Publication J9-/130t, etc. Particularly preferably, the aluminum content is 0.0 in atomic ratio of aluminum to titanium. /j or below, and a combination of a solid titanium trichloride catalyst component containing a complexing agent and an organoaluminum compound, especially an aluminum dialkyl monohalide, and optionally an electron-donating compound such as an ether, ester, etc. is used. It will be done. The power of this solid titanium trichloride catalyst is special! Ichizaltjl issue, same! ! 1♂ltj No.2 Publication, samejj11003 Publication, samej! -2717/publication, same j'j-39/l
, J issue, same! ! - i4to tag issue publication, same! 3−ψ
It is described in the P2YR publication, etc.

The polymerization temperature is 0.degree. Further, a molecular weight regulator such as hydrogen may be used if necessary.

Conventionally known stabilizers, metal damage inhibitors, flame retardants, inorganic or organic fillers, etc. can be added to the polyolefin block copolymer composition of the present invention thus obtained, if necessary.

〔Example〕

Examples will be shown below, but the present invention is not limited to the following examples unless the gist of the invention is exceeded.

Physical property values in the following examples were measured according to the following methods.

(1) Tensile test・・・・・・ASTMDjJf
(Measure tensile modulus, tensile strength at yield point, strength at break and elongation at break) (2) Melt index (Ml)...
・ASTMD-/231 (320°C, 2./Ay> (3) Falling weight impact strength... The polyolefin composite sample used for the measurement was approximately 3.
After being formed into a 0θ μm press sheet, it was heat treated at 200° C./hrO.

The measuring device is a Rheometrics drop tester.
Falling weight height 60.292cm, falling weight weight 3. t/97#,
Measurement was performed at a falling weight speed of 3.3 J J 7 M/S. The measurement temperature is room temperature. The measured value was expressed by dividing the amount of energy required for fracture by the sample thickness. The sample piece has an inner diameter of
, J-inch clamp and measured.

Catalyst production example At room temperature, add N-made toluene to a 1 ton autoclave that has been sufficiently purged with nitrogen! /! Add n-butyl ether t. r. i y (o.rmol), titanium tetrachloride tag. Ty (oz mol) and diethylaluminum chloride 21,tf ((7.
24 Lmol) was added to obtain a brown homogeneous solution. Then, the temperature is raised to 30°C. UO after 30 minutes
The temperature was raised to 4°C and maintained at 4°C for 2 hours. Then 322 titanium tetrachloride (0./7 mol) and/
j, j f tridecyl methacrylate (θ, O j
I mol) was added thereto, and the temperature was raised to f°C. 9r℃
After holding for λ hour, the granular purple solid was separated and washed with toluene to obtain solid titanium trichloride.

Example 1 Et2AICIφ. 7/mmol,
3-Methylbutene/30021 was charged. After raising the internal temperature to lθ℃, the solid titanium trichloride catalyst component obtained in the catalyst production example 8←! ? was pressurized with argon gas to start polymerization. Polymerization proceeded in a slurry state, and unreacted 3-methylbutene/ was purged after -20 minutes. Immediately after completing the purge, prepare the Et2AICI in advance.
/ 'A. / mmo1 and normal hexa7 / 0
A solution of 0.0 Wte was injected under pressure with a propylene gas to start polymerization of propylene. At this time, the polymerization temperature was 70°C,
Propylene was additionally fed so as to maintain the propylene pressure t, 97 cT/t, and polymerization was carried out for 20 minutes.

Polymerization was stopped by adding n-butanol lOO-, and to
The catalyst was decomposed by stirring at ℃ for 3θ minutes.

Unreacted propylene was purged, the temperature was lowered to room temperature, and the solvent was removed by decantation. Furthermore, 1000 rttl of n-hexane and n-7" tanol jo.6 were added and the catalyst decomposition operation was repeated in the same manner. After that, it was thoroughly washed with n-hexane at room temperature. After drying, a white color of 277F was obtained. A polymer powder was obtained.

As a result of measuring the composition using melt 13C-NMR,
The weight ratio of polymer component (A) to polymer component (B) was /A to ♂ψ.

The obtained polymer powder was added with 0.2 parts by weight of Irganox 1010 (trade name) manufactured by Nippon Ciba Geigy, 0.2 parts by weight of Irgafos P-EPQ (trade name), and ta,10-dihydroanthracene as heat stabilizers. Add 0.2 parts by weight, 3
3 using a Dalmage screw in an extruder with a diameter of 0.
The mixture was kneaded twice under the conditions of ψ0°C and 4Z Orpm. Physical properties were measured at 200°C after forming a press sheet at 3ψ0°C.
The measurement was performed after annealing for 1 hour/hour.

Table 1 shows the physical property measurement results. Also. The same sample used for physical property measurements was sufficiently cooled with liquid N2, then broken, and the fractured surface was observed with a scanning electron microscope. The results are shown in Figure 1 (Photo 1a).

From the difference in the photograph, in this example, poly-3-methylbute7-/
It can be seen that they are very finely distributed.

Comparative Example 1 Implementation ψjl-/K: Th, 3-methylbutene-1 was polymerized in exactly the same way, and after purging unreacted monomers, hydrogen as a chain transfer agent was added to prevent the formation of a block copolymer. Gas! #/d tension and held at 70° C. for ψθ minutes to sufficiently promote chain transfer reaction due to hydrogen. Next, the hydrogen gas was purged and replaced sufficiently with argon gas, and then propylene polymerization, physical property measurements, and scanning electron microscope observation were performed under the same conditions as in Example 11.

The results obtained are shown in Table I and Figure 1 (Photo-b). According to Photo 1k, it can be seen that the dispersion of poly-3-methylbutene/ is much poorer than in Example-1.

Example 2 The procedure was carried out using the same equipment as in Example 1. E t 2 AI Cl 3. J j rrzm
O l s 3-methylbutene-73001It6 was charged. After raising the internal temperature to 0° C., the solid titanium trichloride catalyst component 1, θ32η obtained in the catalyst production example was pressed with argon gas to initiate polymerization. Polymerization proceeded in a slurry state, and unreacted 3-methylbutene-1 was purged after 1 hour.

Immediately after purging unreacted 3-methylbutene-1, pre-prepared Et2AICI/Ommol
A solution of 10 oz of normal hexane was injected with propylene gas to initiate polymerization of brobylene. At this time, the time from 3-methylbutene-1 purge to initiation of propylene polymerization was set to 1 minute. The propylene polymerization temperature was 70°C, and the propylene/pressure was 2. θAl'/Cd
Brobylene was additionally fed so as to maintain the temperature, and polymerization was carried out for 30 minutes. After polymerization, ropetanol 10o111
1 was injected under pressure, and the mixture was stirred at tO°C for 30 minutes to decompose the catalyst. Unreacted brobylene was purged, the temperature was lowered to room temperature, and the solvent was removed by decantation. Furthermore, normal hexane 1000p11 and n-butanol j011 were added and the catalytic decomposition operation was repeated in the same manner. Thereafter, it was thoroughly washed with normal hexane at room temperature.

Then, after drying, a 2/Of white polymer powder was obtained.

In addition, when the composition was measured using melt 13C-NMR, the weight ratio of the polymer component (A) composed of 3-methylbutene-1 unit to the polymer component (B) composed of propylene units was ψ7 pairs! It was 3. The obtained polymer powder was kneaded using the same heat stabilizer and procedure as in Examples, and the physical properties were measured. The results are shown in Table 1/.

Example 3 Polymerization, post-treatment, polymer molding, and physical property measurements were carried out under exactly the same conditions as in Example 2, except that the propylene pressure during the propylene polymerization step was changed to ψ, oA1 + 7 crt. It is shown in Table 1.

Example-φ Using the same equipment as in Example 1, 3.30 mmol of Et2AICI and 3.30 mmol of 3-methylbutene-1 ψθO were charged into an autoclave. Internal temperature ♂O℃
After raising the temperature to , the solid titanium trichloride catalyst component /, θl♂η obtained in the catalyst production example was pressurized with argon gas to initiate polymerization. During this period, feed propylene every 1 minute,
Copolymerization was carried out for 0 minutes.

The total amount of propylene fed in three equal parts was calculated based on the amount of polymer produced during the polymerization process. lLw
After completing the copolymerization of 3-methylbutene-1 and propylene, unreacted 3-methylbutene-1 was purged and immediately the previously prepared E
t2AICI/tA. Tammol and normal hexane lθ00. 1 of solution was injected under pressure with propylene gas,
Polymerization of propylene was started. At this time, after purging 3-methylbutene/, the time in the case to start polymerization of brobylene was 2 minutes.

The polymerization temperature of propylene was 70°C, and the propylene pressure was 3.
Propylene was additionally fed so as to maintain θk9/Crn2, and polymerization was carried out for to minutes. The subsequent operations, polymer composition, and physical properties were measured in exactly the same manner as in Example-3. The results are shown in Table I.

Comparative Example 2-6 (Homopolymer Production Example) Thoroughly dried and replaced with argon! Et2AICI in autoclave 4. Tammolb and 3-methylbutene/2. I prepared jt. After raising the internal temperature to ♂O ℃, the solid titanium trichloride catalyst component 2 obtained in the catalyst production example was added.
14Lf was pressurized with argon gas to start polymerization. t
After polymerization for 3 hours at ro °C, n-butanol 300.1
was added to stop the polymerization. The catalyst was decomposed by stirring at tO<0>C for 30 minutes. After purging unreacted 3-methylbutene-1, 1000 ml of n-hexane was added and stirred, followed by decantation to remove the solvent. Furthermore, normal hexane/0 0 0 tI! The catalytic decomposition operation was repeated in the same manner by adding 100 ml of 1% n-butanol. Thereafter, it was thoroughly washed with n-hexane at room temperature and dried to obtain a poly-3-methylbutene homopolymer with a melt index of 0 and Ojjt/10 minutes! ,r! I got 2.

(Homopolymer Production Example-b) Et AICI J, Ill) 4L was thoroughly dried and placed in an argon-substituted induction stirring autoclave with a capacity of 21.
2 mmo 1 and 2000@l of n-hexane were charged. After raising the internal temperature to 70°C, the solid titanium trichloride obtained in the catalyst production example. 23jη was pressurized with argon gas in the presence of propylene to initiate polymerization. brobylene pressure ii. Propylene was additionally fed to maintain the temperature at 7 crI, and polymerization was carried out for 10 minutes. The subsequent steps were carried out in the same manner as in Homopolymer Production Example 1a, and a polypropylene homopolymer jljf was obtained. When 0.6 parts of BHT was added to the obtained polypropylene and the melt flow index at 230°C (measured according to ASTM-D-/J Jr) was measured, o. It was 710 minutes.

Comparative Example 2 To 10 parts of the polymer powder obtained in Homopolymer Production Example 1a, 0.2 parts of Irganox 1010, which was the same as that used in Example 1l, and 0.2 parts of Irgafos P-EPQ were added as heat stabilizers. 2
After adding 0.2 parts of t,10-dihydroanthracene, the mixture was heated to 4'Orpm using a Dalmage screw in a single screw extruder (J(1)Wφ screw diameter).
The mixture was kneaded at JψO<0>C, and the physical properties were measured in the same manner as in Example-2.

Comparative Example 3 Using the polymer powder obtained in Homopolymer Production Example 1b, the same procedure as that described in Comparative Example 2 was used to measure the physical properties.

Comparative Examples 1-6 After mixing the polymer powders obtained in Homopolymer Production Example 1a and Homopolymer Production Example-b at the mixing ratio shown below, the same heat stabilizer as in Example-2 was added. The pellets were made into pellets using the processing method and cross-wire method, and the physical properties were measured in the same manner.

0 Comparative Example-←: Homopolymer Production Example-The weight ratio of a to 1b is 70:30, 0 Comparative Example-Even: Homopolymer Production Example-The weight ratio of a to 1b is jO to jO, 0 Comparison Example 6 = Homopolymer Production Example 1a to -b weight ratio of 30:70 The results of Comparative Examples 2 to 4 are shown in Table 1. Figure 1 (Photo 10) shows the results of electron microscopic observation of the sample obtained at the same comparison time. According to Photo 10, poly-3-methylbutene-1 (homopolymer-a) and polypropylene (Homopolymer-6) was simply blended with Polymer 3.
- Dispersion of methylbutene-1 is as in Example 1l. It is clear that it is far inferior.

Comparative Example 7 Et2AICI/16mm01, normal hexa 7700rxlh, and 3-methylbutene/700td were charged into a 2 t capacity induction stirring autoclave which had been thoroughly dried and purged with argon. After raising the internal temperature to 0.degree. C., argon gas was pressurized into the reactor to initiate polymerization. Simultaneously with the start of the polymerization, propylene was supplied to the liquid phase at a rate of 302/- hours.
Time polymerization was performed. When the post-process was carried out in the same manner as in Example-1, a polymer of /If9 was obtained.

This polymer contained 30 wt% of propylene monomer, and the physical properties were measured using the same procedure as in Example-2.
Melting point 26/℃ and iso℃, tensile modulus も,0 0 0
#/cdl, yield point strength 2.20 #/d1, break point strength 3 or H77, and break point elongation 3 ta.

Reference Example 1 The specified temperature was set in a 2 t capacity induction stirring autoclave which had been thoroughly dried and replaced with argon. of diethylaluminum chloride and 3-methylbutene-1 were charged. Go to internal temperature
After raising the temperature to .degree. C., a predetermined amount of the solid titanium trichloride catalyst component obtained in the catalyst production example was pressurized with argon gas to initiate polymerization. Polymerization proceeded in a slurry state. After polymerization for a predetermined period of time, about 10° of n-butanol was added to stop the polymerization, and unreacted 3-methylbutene-1 was removed. Subsequently, normal hexane lt was added, and the mixture was stirred for 3θ minutes at to°C to completely decompose the catalyst, and then the temperature was lowered in a room temperature cabinet, and the supernatant liquid was removed. Furthermore, normal hexane lttJ at room temperature
After stirring, remove the supernatant liquid! After repeating the process several times, a white polymer powder with a titanium content of /Oppm or less was obtained. Obtained polymer powder 10
0 parts, 0.2 parts of Irganox 1010 similar to that used in Example 1 as a heat stabilizer, and Irgafos P-EP.
0.2 parts of Q, and 0.2 parts of ta,10-dihydroanthracene. After adding λ part, Meltoy/Dex (320℃,
Ko. /5c9 load in accordance with ASTM D-/2jl). The polymerization conditions (catalyst amount, polymerization time) were changed as shown in Table 1, A to H. Polymerization results A-Hfe are shown in Table-2. Based on these results, Figure 2 shows the relationship between polymerization time and melt index. As is clear from FIG. 2, in the 3-methylbutene-1 polymerization step, the melt index decreases over time for several 10 minutes from the start of polymerization. In other words, it shows that the molecular weight of the produced polymer increases over several tens of minutes from the start of polymerization. That is, this shows that the catalyst active sites remain alive for several 10 minutes, and therefore, a block copolymer is produced by switching the polymerization monomer during this period.

Reference Example-2 Polymer J obtained in Example 1. A 7 4 9? was extracted using a Soxhlet extractor under xylene reflux for 74 hours, and as a result, 74'wt% was extracted into xylene. When the melting point of this extract was measured using a differential scanning calorimeter (OSC), only peaks at /1 and 2°C were observed. On the other hand, the melting point of the extraction residue (4 wt%) was similarly measured by DSC and was found to be 307°C and /jψ
A peak was observed at °C. This extraction residue is further processed using the method described above. Although extraction was carried out for 20 hours, no elution of the polymer into the extraction solvent xylene was observed. From the above results, it was found that /Owt% of unextractable polymers were present in the extraction residue. Reference Example-3 The blend of Comparative Example-6 was extracted in the same manner as Reference Example-2. As a result, despite the extraction time of 27 hours, 62.4'wt% was extracted into the extraction solvent xylene. The melting point of this extract was measured using DSC.
Only the peak at t3°C was observed. On the other hand, j O. 6
Results of similarly measuring the melting point of wt% extraction residue 30
Only a peak at 1°C was observed.

l [Effects of the Invention] The polyolefin block copolymer composition according to the present invention has excellent heat resistance and rigidity, as well as excellent impact resistance. It is excellent in that the molding shrinkage rate and shape shrinkage rate anisotropy, which were major drawbacks, are improved. In addition to primary properties, it also has excellent electrical properties, chemical resistance, and moisture absorption resistance.

[Brief explanation of drawings]

Figure 1 is a photograph (x2000x) of the fractured surface of a polymer obtained in an example of the present invention taken by a scanning electron microscope.
, representing the particle structure of the polymer. In the figure, 〉a〉 is obtained in Example-/, and <b> is obtained in Comparative Example-/
c) was obtained in Comparative Example-2. FIG. 2 is a diagram showing the relationship between polymerization time and melt index in the polymerization step of 3-methylbutene-1 shown in Reference Example 11 of the present invention. Ko 2 Otori fL 金＠ま(intervention) Procedural Dispute Manual (Method) October 12, 1999 Patent Application No. 164442 2 Title of Invention Polyolefin Block Copolymer Composition and Process for Producing the Same 3 Amendment Related patent distributor (596) Mitsubishi Kaoru Co., Ltd. 4 Agent 100 2-5-2-5 Marunouchi, Chiyoda-ku, Tokyo Date of amendment order: September 26, 2010 (shipped) (Japanese) 6 Drawings to be amended 7 Contents of the amendment Replacement of Figure 1 as shown in the attached sheet

Claims (2)

[Claims] (1) Crystalline polymer component (A) consisting of repeating units containing 80 wt% or more of 3-methylbutene-1 unit and 90 wt% or more of α-olefin units having 2 to 10 carbon atoms excluding 3-methylbutene-1. A composition containing a crystalline polymer component (B) consisting of a repeating unit comprising:
At least a part of the polymer component (A) and a part of the polymer component (B) constitute a block copolymer, and the ratio of polymer component (A) to polymer component (B) in the composition is The polymerization ratio of is in the range of 90:10 to 10:90, and 3
Melt index measured at 20℃ is 0.001-10
A polyolefin block copolymer composition in the range of 00 g/10 min. (2) Crystalline polymer component (A) consisting of a repeating unit containing 80 wt% or more of 3-methylbutene-1 unit and 3
- A composition containing a crystalline polymer component (B) consisting of repeating units containing 90 wt% or more of α-olefin units having 2 to 10 carbon atoms excluding methylbutene-1, the composition comprising at least the above polymer component (B). Part of A) and polymer component (
A part of B) constitutes a block copolymer, and the polymerization ratio of polymer component (A) to polymer component (B) in the composition is in the range of 90:10 to 10:90, and 32
Melt index measured at 0℃ is 0.001-100
In producing a polyolefin block copolymer composition in the range of 0 g/10 min, the above polymer is produced from a monomer mainly composed of 3-methylbutene-1 in the first polymerization step in the presence of a coordination polymerization catalyst. The combined component (A) is polymerized, and then immediately in a second polymerization step, the above polymer component (B) is obtained from monomers mainly composed of α-olefins having 2 to 10 carbon atoms excluding 3-methylbutene-1. 1. A method for producing a polyolefin block copolymer composition, the method comprising carrying out multistage polymerization including at least two polymerization steps of polymerizing a polyolefin block copolymer composition.