JPS59157107A - Crosslinked olefin block copolymer - Google Patents

Abstract

PURPOSE:To provide titled copolymer of specific solubility and fluidity, having high heat and low-temperature impact resistance and settability, comprising a 4-methylpentene-1 polymer block and a random copolymer one consisting of 4- methylpentene-1 and another alpha-olefin. CONSTITUTION:The objective copolymer comprising (A) 5-50pts.wt. of a 4- methylpentene-1 homopolymer block plus copolymer block containing >=60wt% of 4-methylpentene-1 such as a random copolymer block consisting of 4-methylpentene-1 and another 2-12C alpha-olefin and (B) 50-95pts.wt. of a random copolymer block containing 30-85wt% of ethylene and consisting of ethylene and 4- methylpentene-1 or another 3-12C alpha-olefin. This copolymer has the following characteristic values: (1) hot xylene insolubles: 5-75wt% (2) fluidity at 250 deg.C under a load of 30kg: 3-1,000(cc/secX10<-3>) (using Koka-shiki Flow Tester with a cylinder diameter of 10mm., an orifice diameter of 1mm., and an orifice height of 2mm.).

Description

[Detailed Description of the Invention] [1] Background of the Invention The present invention relates to a partially crosslinked olefin block copolymer that has excellent heat resistance, flexibility, tensile strength, low-temperature impact resistance, processability, and setting property. .

In recent years, there has been a growing demand for soft materials that have excellent heat resistance (especially shape retention against external forces at high temperatures), low-temperature impact resistance, tensile strength, moldability, and appearance for automobile parts, electrical product parts, electrical cable covering materials, etc. Expectations are rising. Soft materials include polyvinyl chloride with plasticizers, ethylene-vinyl acetate copolymers, and ethylene-α-olefin copolymers (medium- and low-density polyethylene, etc.), but these have low flexibility, processability, and low-temperature properties. Although it is a material with excellent impact resistance, it has poor heat resistance and rubber elasticity (setting properties).

In addition, random copolymers of propylene and other olefins are materials with improved heat deformation resistance compared to those materials, but they still do not work well at high temperatures (generally above 150°C, especially above 160°C).
It is a material that has poor heat resistance (shape retention against external forces) at temperatures above 30°F (°C or higher), and poor impact resistance, rubber elasticity (setting properties), and flexibility at low temperatures.

In addition, polyolefin thermoplastic elastomers, such as those found in JP-A-49-53938 and JP-B-53-34210, are used as materials with excellent flexibility, low-temperature impact resistance, rubber elasticity, heat resistance, and moldability. There is. this is,
Polypropylene resin as a hard segment and polyolefin rubber (especially ethylene-propylene rubber) as a soft segment are melt-kneaded, and the rubber portion is partially melted during melt-kneading in order to develop heat resistance and rubber elasticity. Crosslinked materials have mainly been studied and put into practical use. However, these materials still lack sufficient heat resistance (shape retention) at high temperatures, and require an additional process of melting and kneading the two components, which significantly increases costs. There are problems with the manufacturing process.

Also, Japanese Patent Application No. 130730/1983,
The crosslinked olefin block copolymer previously proposed in No. 8817, T￥F Application No. 56-202059, and Japanese Patent Application No. 57-69629 has excellent flexibility, heat resistance, moldability, and tensile strength. It is a revolutionary material among existing soft materials in terms of its quality balance of low-temperature impact resistance, rubber elasticity (setting ability), and manufacturing cost.

However, the heat resistance is still insufficient at extremely high temperatures of 150° C. or higher, particularly 1.60° C. or higher.

In view of these current circumstances, the present inventor has developed a method that can be used in extremely high temperature regions of 150°C or higher, especially 160°C or higher, and has low-temperature impact resistance, moldability, tensile strength, rubber elasticity (setting properties), flexibility, and appearance. As a result of intensive research to develop a polyolefin-based soft material with excellent
This has led to the present invention.

(1. Summary of the Invention The present invention provides a 4-methylpentene-1 homopolymer block and a 4-methylpentene-1 and 4-methylpentene-1 homopolymer block.
5 or more and less than 50 parts by weight of block (4) containing 1100 to 60% by weight of 4-methylpentene-1 selected from random copolymer blocks with C2 to C12 α-olefins other than 1, and ethylene content of 30 to 85% by weight of ethylene and C3 to C12 α- other than 4-methylpentene-1
A crosslinked product of an olefinic block copolymer containing a random copolymer block (B) with an olefin and/or 4-methylpentene-1 of 50 or more but less than 95 polymeric moieties, comprising the following (1) and It is a crosslinked olefin block copolymer having the characteristics (2).

(1) Content of thermal xylene insoluble components is 5 to 75% by weight
That's it. (2) The fluidity (amount of resin flowing out from the orifice per second, [ω/sec The crosslinked product has the thermal xylene insolubility as described in (1) above, which reflects the degree of crosslinking, and the fluidity during melting as described in (2) above, that reflects moldability, and has an Olzen bending rigidity (at 10° angle) of 3500 to 9. Flexibility below /i and 40V4/ly/I
It has a tensile strength of 30% or less and a heat resistance of 50% or less in terms of heat and pressure deformation rate (measurement method described later).
It exhibits low-temperature impact resistance of 15 K4-cm/cj1 or more with the following permanent set (measurement method described later) and Charpy impact strength measured at -20°C.

rllll Detailed Description of the Invention l Block Copolymer (1) Composition The block copolymer according to the present invention comprises a 4-methylpentene-1 homopolymer block and a 4-methylpentene-1
and 5 or more but less than 50 parts by weight of one or more blocks (4) selected from random copolymer blocks with C2 to C12 α-olefins other than 4-methylbenzone-1, and ethylene and 4-methyl. C3 other than Penten-1
-C12 α-olefin or (and) 50 or more and less than 95 parts by weight of one or more random copolymer blocks (6) with 4-methylpentene-1.

The block copolymer according to the present invention contains one or more of each block (4) and (B), but there are no restrictions on the arrangement of each block. However, it is preferred that block (4) is generated first, followed by block 0).

The block is formed by homopolymerization of 4-methylpentene-1,
Alternatively, it refers to a portion produced by polymerization under conditions where one or more C2 to C12 α-olefins other than 4-methylpentene-1 and 4-methylbenzone-1 are simultaneously present.

Block ω) Under conditions where ethylene and one or more of 03 to C12 α-olefins other than 4-methylpentene-1 are present simultaneously, or under conditions where ethylene and 4-methylpentene-1 are simultaneously present. or Ca=Ctz other than ethylene and 4-methylpentene-1
It refers to the part produced by polymerization under conditions where one or more of the α-olefins and 4-methylpentene-1 are simultaneously present.

Such a block copolymer is composed of a homopolymer block, a stranded copolymer block, or a random copolymer block having a composition consisting of a random copolymer block and a random copolymer block having a different composition coexisting in one polymer molecular chain. The block copolymer according to the present invention may contain one or more blocks (4) with a weight of 5 or more, a physical mixture of both molecular chains, or a mixture thereof. part by weight, preferably 10 or more and less than 50 parts by weight, more preferably 15 or more and less than 50 parts by weight.
50 or more and less than 95 parts by weight, preferably 50 or more and less than 90 parts by weight, and more preferably 50 or more and less than 85 parts by weight, of one or more blocks (B).

The block (-) is a part that has the characteristics of a crystalline thermoplastic resin, and the block (B) is a part that has rubber-like properties with poor quality or low crystallinity.

If the content of lock (A) is below the above range, the strength and heat resistance will decrease, and the moldability after crosslinking will be poor. On the other hand, if the content of block (2) exceeds the above range, sufficient flexibility will not be exhibited.

The content of 4-methylpentene-1 in the block is 1
00 to 60% by weight, preferably 100 to 70% by weight, more preferably 100 to 75% by weight. Block (4
) If the content of 4-methylpentene-1 is below the above range, the heat resistance will decrease, which is not preferable. In particular, when heat resistance is important, the 4-methylpentene-1 content is 100.
It is preferable to set it as a weighted percentage.

In addition, if flexibility is important even if heat resistance is sacrificed to a certain extent, 4-methylpentene-1
All you have to do is lower the content. Especially 4-methylpentene-1
When copolymerizing with ethylene, the preferable 4-methylpentene-1 content is 92 to 98 double digits %.

α-olefins that can be copolymerized with 4-methylpentene-1, ethylene, phlopylene, butene-1, pentene-1
1, linear α-olefins such as hexene-1, heptene-1, octene-1 and decene-1, and 3-methylbutene-1,3-methylpentene-1,3-ethylpentene-1,3-methylhexene -1,4,4-dimethylpentene-1,4-methylhexene-1,5-)tylhexene-1,5,5-dimethylhexene-1,3,5
Branched α-olefins such as -dimethylhexene-1,3,5,5-,) dimethylhexene-1 are applicable.

Among these monomers, ethylene, propylene, butene-1, hexene-1, octene-1,
It is a 02 to C12 linear α-olefin such as decene-1. Particularly preferred are ethylene, furopylene, butene-1 and hexene-1.

Block (2) is ethylene and α-olefin of 03-C1z or (and) 4-methylpentene-1 tonola, preferably more than 35% by weight and less than 75% by weight, more preferably 40% by weight.
It is more than 70% by weight or less. Since the block (B) must have rubbery properties of poor quality or low crystallinity, if the ethylene content exceeds the above range, the crystallinity will be too high and the flexibility and rubber elasticity will be insufficient. Conversely, if the ethylene content is below the above range, the impact strength at low temperatures may be insufficient, and comonomers such as propylene, 4-methylpentene-1, and butene-1 may themselves form crystalline homopolymers. In some cases, the crystallinity of block (B) becomes too high.

For the same reason, the ethylene content in the block copolymer is 15 to 81% by weight, preferably 17.5 to 6% by weight.
It is 8% by weight, more preferably 20 to 60% by weight.

The 03 to C12 α-olefins other than 4-methylpentene-1 that can be copolymerized with ethylene in block (B) include propylene, butene-1, hentene-1, hexene-1, heptene-1, octene-1 and decene-1
linear α-olefins such as 3-methylbutene-1,3-methylpentene-1,3-ethylpentene-
1,3-Methylhexene-1,4,4-dimethylpentene-1,4-methylhexene-1,5-methylbutene-1.5.5-dimethylhexene-1,3,5-dimethylhexene-1.3. 5.5-) dimethylhexene-1
This applies to branched α-olefins such as

Among these monomers, IH chain α of c3 to c1□ such as propylene, butene-1, hexene-1, octene=1, etc.
-Olefins are preferred.

Nipropylene, butene-1 and hexene-1 are preferred.

(2) Molecular weight The molecular weight of the block copolymer before crosslinking is ASTM-D-
250℃ measured in accordance with 123'8-65T 5
MF'I at K9 load is 0.01 to 1000 (v/]0
m1n].

When the molecular weight exceeds or falls below the above range, it is difficult to obtain a balance between initial moldability and mechanical strength after crosslinking.

2. Production of block copolymer The block copolymer according to the present invention has a content of (a) 4-methylpentene-1 of 100 to 60% by weight, preferably 100 to 70% by weight, in the presence of a stereoregular polymerization catalyst. , more preferably 1
Selected from a 4-methylpentene-1 homopolymer block of 00 to 75 weight or a random copolymer block of 4-methylpentene-1 and an α-olefin of c2 to c1□ other than 4-methylpentene-1. One or more of the unblocked prisoners to 5 or more and less than 50 heavy religions, preferably 1
0 to less than 50 parts by weight, more preferably 15 to less than 50 parts by weight; and (b) ethylene content of 30 to 85% by weight, preferably 35% by weight.
~75% by weight, more preferably 40 to 70% by weight of ethylene and α of 03 to C12 other than 4-methylpentene-1
- Block (B) selected from random copolymer blocks with olefin and/or 4-methylpentene-1
It can be produced by combining steps of producing 50 or more and less than 95 parts by weight, preferably 50 or more and less than 90 parts by weight, of one or more of the following.

Either of steps (a) and (b) may be performed first. This does not exclude the inclusion of a small proportion of other polymerization steps before, during, or after (a) and (b), if necessary.

A suitable stereoregular polymerization catalyst for use in the present invention is, for example, a catalyst mainly consisting of a titanium component and an organoaluminum compound.

As the titanium component, a titanium compound supported on a carrier such as α, β, r or δ type titanium trichloride or magnesium chloride is used. In particular, titanium trichloride obtained by extracting and removing aluminum chloride using a complexing agent from titanium trichloride obtained by reducing titanium tetrachloride with organoaluminium, activated by an appropriate method, magnesium chloride, etc. It is preferable to use a carrier on which a titanium compound is supported as the titanium component of the catalyst, from the viewpoint of obtaining a high yield with respect to the catalyst and from the viewpoint of making block 03) more rubbery.

As an organoaluminum compound, the general formula AotRaY3-
It is preferable to use a compound represented by a.

a is a number such that o<ti and 7 is a number, Y is an atom or an alkoxy group, and R is a C1-18 hydrocarbon residue, preferably an alkyl group or an aryl group.

Specifically, triethylaluminum, diethylaluminum chloride and the like are preferred.

A small amount of an electron donor may be combined as a third component in the catalyst consisting of a combination of these two essential components. As the electron donor, organic acid ester, ether, fmin,
Alcohols, ketones, aldehydes, phenols, etc. are used. Specific examples of electron donors that can be used in the present invention can be found, for example, in JP-A-54-158489.

Polymerization can be carried out either continuously or batchwise. When carrying out the process in a continuous manner, one or more polymerization tanks are used for each of the steps (a) and (b), and each reaction is carried out under steady conditions. In the batch method, the next step is started after all or a predetermined amount of the monomer in each step has reacted, but once the predetermined amount of monomer has reacted, some or all of the unreacted monomers are removed from the tank. You can also move on to the next process after sending it out.

The method of the present invention is usually carried out at a polymerization temperature of 0 to 200°C and a polymerization pressure of 0 to so Kg/y/l (gauge pressure). A slight negative pressure (gauge pressure) is allowed. Hydrogen can be used to control the molecular weight of the copolymer. It is also permissible to vary the hydrogen concentration between each step to cause a difference in the molecular weight of the copolymer blocks produced therein.

The polymerization may be carried out in a monomer of 4-methylpentene-1 or in an inert hydrocarbon solvent such as n-hebutane or n-hexane.

3. Crosslinked product of block copolymer The crosslinked product of the present invention is derived from an olefinic block copolymer, and the block copolymer is as explained in the previous section. This crosslinked product is mainly a block of the copolymer (an evenly equivalent portion is involved in crosslinking,
It is thought that the portion corresponding to block (4) hardly participates in crosslinking and contributes to imparting fluidity to the crosslinked product when melted.

Therefore, the present crosslinked product can be considered to have a so-called partially crosslinked structure. It goes without saying that such a partially crosslinked structure is naturally caused by the chemical structural characteristics of the block copolymer that is its precursor. The part corresponding to the block (4) that does not participate in crosslinking and imparts fluidity to the crosslinked product has a 4-methylpentene-1 segment with a high melting point, and is a low crystalline component and has rubbery properties. It is thought that the fact that the block (6) is crosslinked is the reason why this crosslinked block copolymer exhibits an excellent balance between heat resistance and moldability (fluidity).

The fact that this crosslinked product is partially crosslinked and has excellent moldability is due to the gel fraction measured as a hot xylene insoluble component and the melt flowability under high shear stress measured with a Koka type flow tester. recognized by.

That is, the crosslinked product of the present invention contains 5 to 75% by weight, preferably 10 to 65% by weight of a hot xylene-insoluble component (gel).
More preferably, the content is 20 to 60% by weight. If the gel fraction is below the above range, the heat resistance will be insufficient and the product will return.
Moreover, when the amount exceeds the above range, moldability is impaired. To measure the thermal xylene gel fraction, use a Soxhlet extractor, set a sample 1f cut as small as possible wrapped in an 80-mesh wire mesh, and reflux 755-300 g of p-xylene.
This is done by extracting for 10 hours under conditions that occur approximately once every 0 minutes.

The melt flowability of the crosslinked product of the present invention was measured using a Koka type flow tester under the following conditions (resin equivalent per second flowing out from ground ice (ec/second x 40-3)).
) is 3 to 1ooo, preferably 5 to 700, more preferably 10 to 500. When the fluidity is below the above range, moldability becomes difficult. Exceeding the above range is not a problem per se, but it is usually unfavorable as it causes a decrease in gel fraction and impairs heat resistance and mechanical properties.

4. Production of crosslinked product Any known technique can be applied as a method for obtaining a crosslinked product. A typical example is a mechanical melt-kneading method, in which general melt-kneaders such as screw extruders, twin-screw extruders, and Banbury mixers are used, and partial crosslinking is performed by a known method at the melt-mixing stage. can do. After impregnation with a crosslinking agent, it is possible to crosslink by heat or by radiation.

Furthermore, it is preferable to use a crosslinking aid in order to achieve efficient crosslinking, uniform crosslinking density, and good appearance and balance of physical properties. The method of partially crosslinking using a crosslinking aid includes adding a crosslinking aid to the olefin block copolymer and uniformly dispersing it, then adding a crosslinking agent and melt-kneading to partially crosslink; Alternatively, a crosslinking aid and a crosslinking agent are simultaneously added to the olefin block copolymer and melt-kneaded, or a crosslinking aid is added to the olefin block copolymer and dispersed uniformly, and then the crosslinking agent After adding and dispersing the olefinic block copolymer, statically partially crosslinking by raising the temperature to a temperature higher than the decomposition temperature of the crosslinking agent, or adding and dispersing the crosslinking agent and the crosslinking agent simultaneously to the olefin block copolymer,
There is a method of statically partially crosslinking by raising the temperature above the decomposition temperature of the crosslinking agent. In the above step, a step of uniformly dispersing the crosslinking agent in the block copolymer, 'dispersing the crosslinking agent in the olefin block copolymer, and further static crosslinking by raising the temperature to a temperature higher than the decomposition temperature of the crosslinking agent. A solvent may be present in the step.

As the crosslinking aid, various unsaturated compounds, sulfur, etc. are used. Specifically, liquid 1,2-polybutadiene having a double bond in the side chain or main chain, liquid 1,2-polybutadiene,
, 4-polybutadiene, liquid polybutadiene containing a mixture of 1,2 bonds and 1.4 bonds, and modified products thereof, oligomers such as liquid styrene-butadiene rubber, liquid nitrile-butadiene rubber, liquid chloroprene rubber, side chains, etc.) Syndiotactic 1,2-polybutadiene, 1,4-bolybutadiene with a double bond in the main chain
En rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polymers such as polyisobutylene, divinylbenzene, lauryl methacrylate, ethylene dimethacrylate, diaryl hepta-maleate, diaryl phthalate, maleimide, phenylmaleimide,
N+N'-m-7 enylene bismaleimide, N, N'-
Various divinyl compounds such as m-phenylenebismale f-mide, acrylamide, maleic anhydride, vinyl compounds, compounds having three or more hinyl bonds, p-quinonedioxime, p,p'-dibenzoylquinonedioxime, etc. Oxime compounds and the like are used. Among these, liquid 1,2-polybutadiene, liquid 1,4-polybutadiene, liquid polybutadiene containing a mixture of 1,2 bonds and 1,4 bonds, modified products thereof, and divinylbenzene are preferred. In particular, liquid 1,2-polybutadiene is preferred from the viewpoint of crosslinking efficiency and obtaining a good balance of physical properties.

As the crosslinking agent, conventionally known crosslinking agents such as aromatic or aliphatic peroxides or azo compounds are used. Specifically, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-sibide lobaroxide,
1,1.3. Hydroperoxides such as 3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, 1
-butylcumyl peroxide, 2,5-dimethyl-2
, 5-di(t-butylperoxy)hexane, dicumyl peroxide, α,α'-bis(t-butylperoxyinglobil)benzene, peroxy)butane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy) 3,3.
Peroxyketals such as 5-trimethylcyclohexane, di-t-butylciba-oxyinphthalate, t
- Peroxy esters such as butylperoxybenzoate, t-butylperoxyacetate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyisopropyl carbonate, benzoyl peroxide , diacyl peroxides such as acetyl peroxide, propionyl peroxide, stearoyl peroxide, and hiscyclohexanone peroxide. - These crosslinking agents may be used alone or in combination of two or more. Further, these crosslinking agents may or may not be diluted with an inert diluent such as calcium carbonate.

During crosslinking, particularly during mechanical melt-kneading, a crosslinking reaction retardant may be used as necessary to make the crosslinking uniform and to control the crosslinking reaction. Such retardants include -hydroquinone, 2,6-di-t-butyl-p-cresol, t-butylcatechol, 4,4'
-butylidenebis(3-methyl-6-t-butylphenol), 2,27-methylenebis(4-methyl-6-
t-butylphenol), 4,4'-thiobis(6-t
-butyl-3-methylphenol), mercaptobenzothiazole, dibenzothiazole disulfide, 2,
2゜4-) I77'-f-ru-1,2-dinorhodroquinone polymer, phenyl-β-naphthylamine, N-
N'-di-β-naphthyl-p-phenylenediamine, N
- There are organic peroxide crosslinking scorch inhibitors such as nitrosodiphenylamine. Also, fillers such as carbon and white pigments, paraffinic or naphthenic process oils, Wax, plasticizers such as dioctyl phthalate, pigments, etc. may be blended. Further, additives such as a heat stabilizer, an antioxidant, and an ultraviolet absorber may be added as necessary.

Examples In the Examples and Comparative Examples below, unless otherwise specified, the test methods used to evaluate each product are as follows.

(1) Melt flow index (250°C, 5.0 initial load) ASTM-D-1238 (t/10 minutes) (2) Olzen bending rigidity (10° angle) ASTM-D-747 (Kg/, 4) Sample: 211II+ thickness press sheet (3) Tensile strength JIS-6301 (Kg/d) Test piece No. 3 sample Injection molded sheet 2fi thick (4) Tensile elongation JIS-6301 (%) Test piece Type 3 (5) Fluidity (measure of formability) In a Koka-type flow tester, a sample was placed in a cylinder with a diameter of 10 m, heated to 250°C, a load of 30 ~ was applied, and a It is obtained by the amount of resin flowing out per second from an orifice of diameter x 2 m high.

(' x 10-3 CC/sec) (6) Heating and Pressure Deformation Rate A sample (1 t
Attach MX 1 (*X 2 day thick press sheet), temperature 160℃, load 3 K9/cr! 1 hour, the load was removed, and the thickness deformation rate was obtained after 10 minutes.

[%] (7) Gel fraction (content of hot xylene-insoluble components/scale of degree of crosslinking) Sample 12 was wrapped in an 80-mesh stainless steel wire mesh, placed in a Soxhlet extractor, and heated with 30% hot p-xylene.
After extraction for 10 hours while refluxing at a frequency of about once a minute, the weight ratio of the unextracted portion to the prepared sample is determined.

(8) Charpy impact strength [first-tyn/ad
] JIS-7111 (Sample: 2-thick press sheet, 3 sheets with 11° notches. Measurement temperature at knee 20°C) Example A-1 Internal volume with stirring blades 1. After sufficiently purging the interior of the Ot stainless steel reactor with N2 gas, n- was used as the polymerization solvent.
Added 2 parts of hebutane. The temperature inside the vessel was maintained at 30°C, and diethylaluminum chloride (DEAC)2 was used as a catalyst.
．． Oy, and titanium trichloride (T manufactured by Marubashira Nlupei Chemical Co., Ltd.
BB-19) Added 0.4 Of. Subsequently, 4-methylpentene-1 and 2 were added.

The temperature inside the vessel was immediately raised to 70°C, and the inside of the system was pressurized to 1.0 Kg/tri (gauge pressure) with N2. Furthermore, 1-5 t (in terms of STP) of hydrogen was added.

The reaction was carried out for 2 hours and 30 minutes while maintaining the inside of the system at 70°C.

(Block A, 4-methylpentene-1 (lDj4
(autopolymerization) Next, 2 portions of n-hebutane were added and the temperature inside the vessel was raised to 65℃.
In addition to setting ethylene, propylene, and hydrogen to 85
It was supplied over a period of 3 hours and 30 minutes at a rate of 1/hour, 452/hour, and 0.811 hour (STP conversion).

(Production of block B (ethylene/propylene/4-
Methylpentene-1 copolymerization) The obtained block copolymer was purified with alcohol to obtain a dry product.

Table 1 shows the proportion and composition of each block in the obtained copolymer. However, since it is difficult to calculate the production ratio and composition of each block from this experiment alone, the intermediate polymerization stage was separately carried out under the same conditions as in this example, and then the catalyst was immediately decomposed. The weight and composition of the polymer obtained by purification and drying under the same conditions as above were measured, and the calculations were made indirectly on the assumption that these also apply to each polymerization step in this implementation ψU. Also, the composition is
Measured by carbon 13 NMR.

Example B-1 A pressurized kneader for rubber having a capacity of It was set at 250°C, and 93 parts by weight of the block copolymer of Example A1 and liquid 32-polybutadiene (Nl manufactured by Nippon Soda Co., Ltd.) were added as a crosslinking aid.
5SOIPB B-3ooo) 7 parts by weight,
After melt-kneading for a minute, 0.4 parts by weight of peroxide (Pa-Kadox 14 manufactured by Kayaku Nouri Co., Ltd.) was added as a crosslinking agent.
The block copolymer was further melt-kneaded for 5 minutes to crosslink the block copolymer.

Table 2 shows the results of evaluating the physical properties of the product.

Example A-2 In Example A-1, in the polymerization of the block pellets, 4-methylpentene-1 and 2 were added, the temperature inside the vessel was immediately raised to 65°C, and the system was heated to 1.0 kg/g of gold using N2. The pressure was increased to cJG as much as possible, 1.2 t of hydrogen (STP equivalent) was added, the inside of the system was maintained at 65°C, and ethylene was supplied at a rate of 6 r/hour from 15 minutes later, and the reaction was carried out for 2 hours. Block copolymerization was carried out under the same conditions as in Example A-1, except that block (6) was polymerized for 4 hours.

The results are shown in Table 1.

Example B-2 The copolymer of Example A-2 was used as the raw material copolymer, and Perkadox 1 manufactured by Kayaku Nury Co., Ltd. was used as the peroxide.
Example B- except that 0.5 parts by weight of 4 was added.
Crosslinking treatment was carried out under the same conditions as in 2.

The results are shown in Table 2. ◎ Example A-3 In Example A-2, propylene was supplied instead of ethylene at a rate of 15 t/hour in the polymerization of block A.
The reaction was carried out for 3 hours. In the polymerization of block (B), ethylene, propylene, and hydrogen were added at 70y/hour, 4
Block copolymerization was carried out under the same conditions as in Example A-2, except that the supply was carried out at a rate of 9 v/hr, X, Ot/hr over 3 hours and 30 minutes.

The results are shown in Table 1.

Example B-3 95 parts by weight of the copolymer of Example A-3 as a raw material copolymer and 5 parts by weight of liquid 1,2-polybutadiene (Nl5SOPB B-3000, manufactured by Nippon Soda Co., Ltd.) as a crosslinking aid were charged. The crosslinking treatment was carried out under the same conditions as in Example B-1, except that 0.4 parts by weight of peroxide (Parkyoku Dox 14, manufactured by Kayaku Nury Co., Ltd.) was added as a crosslinking agent.

The results are shown in Table 2.

Comparative Example A-1 After sufficiently replacing the inside of the same reactor as in Example A-1 with propylene, 3.5% of n-hebutane was added as a polymerization solvent.

The temperature inside the vessel was maintained at 30° C., and 2.02 y of diethyl aluminum chloride (DEAC) and 0.40 y of titanium trichloride (TBB-19, manufactured by Marubashira Tsurubei Chemical Co., Ltd.) were added as catalysts. The temperature inside the vessel was immediately set to 65°C, and propylene was supplied at a rate of 100 t/hour and hydrogen was supplied at a rate of 117 hours over a period of 2 hours and 30 minutes.
1 for 1 hour and 30 minutes at a speed of 60 ohm/hour (the above is the polymerization of block A. Random copolymerization block of propylene and 4-methylpentene-1), and then the unreacted gas in the vessel was brought to 0 pressure in the vessel. .4. Discharge until Kg/c++f (gauge pressure) is reached, set the temperature inside the vessel to 65℃, and discharge ethylene, propylene, and water g't-65t/hour each, 45t.
/hour, 1. 3 hours 3 at speed IW at O11 (STP conversion)
The mixture was fed for 0 minutes to cause a reaction. (Block B
: ethylene/propylene/4-methylpentene-1 random copolymer block) Purification of the obtained block copolymer and analysis of the composition were all carried out in the same manner as in Example A-1. The results are shown in Table 1.

Comparative Example B-1 The crosslinking treatment was carried out under the same conditions as in Example B-1 except that the block copolymer prepared in Comparative Example A-1 (4) was used.

The results are shown in Table 2.

Comparative Example A-2 In the polymerization of block (B), ethylene, propylene and hydrogen were each fed at 20 t/hour, l 1097 hours, 0.
Polymerization was carried out under the same conditions as in Example A-1, except that the polymer was supplied at a rate of 5 t/hour (STP equivalent). The results are shown in Table 1.

Comparative Example 13-2 All Example B except that the copolymer of Comparative Example A-2 was used.
Crosslinking treatment was performed under the same conditions as in -1.

The results are shown in Table 2.

(Margin below)

Claims (1)

[Claims] 4-methylpentene-1 homopolymer block and 4-
C other than methylpentene-1 and 4-methylpentene-1
4-methylpentene-1 content selected from random copolymer blocks with 2-C12 α-olefins 100-100
5 or more and less than 50 parts by weight of 60% by weight block (4);
And, ethylene with an ethylene content of 30 to 85% and 4-
Crosslinking of an olefinic block copolymer containing 50 or more and less than 95 parts by weight of a C3 to C12 α-olefin other than methylpentene-1 and/or a random copolymer block with 4-methy, rubentene-1 A crosslinked olefin block co-backing polymer, which is characterized by having the following properties (1) and (2). (1) Contains 5 to 75% of hot xylene insoluble components
To be. (2) The fluidity (resin mass flowing out from the orifice per second (cc/sec Xl0-3)) measured under the following conditions using a Koka type flow tester is 3 to 1000. Cylinder diameter: 10mm; Orifice diameter: 1, m+ei;