JPH0314810A - Method for producing crosslinked olefin block copolymer - Google Patents

Abstract

PURPOSE:To improve the balance among flexibility, strength and processability of a specified olefin block copolymer by crosslinking. CONSTITUTION:An olefin block copolymer composed of 5-50wt.% block (A) selected from among PP, propylene-ethylene random copolymer or propylene-4-12 C alpha-olefin random copolymer and having a propylene content of 75-100wt.% and 95-50wt.% block (B) comprising an ethylene-4-12C alpha-olefin-ethylene block copolymer having an ethylene content of 30-85wt.% and a weight ratio of 4-12C alpha-olefin to propylene of at least 1 is melt-kneaded in the presence of a crosslinking agent, e.g. t-butyl peroxybenzoate, to give a crosslinked olefin block copolymer having a hot xylene insolubles content of 5-75% and a fluidity (the amount of resin flowing out of an orifice per second) of 3-200cc/secX10<-3> as determined with a Koka type flow tester under the conditions of a cylinder diameter of 10mm, an orifice diameter of 1mm, an orifice height of 2mm, a load of 30kg, and a resin temperature of 200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention The present invention provides a partially crosslinked polymer with excellent heat resistance and setting properties derived from an olefinic block copolymer with an excellent balance of flexibility, strength, and processability. relating to things.

In recent years, expectations have been increasing for soft materials with excellent heat resistance (particularly shape retention against external forces at high temperatures) and strength for automobile parts, home appliance parts, electric cable covering materials, pipes, and the like. Since these materials have physical properties comparable to or close to those of vulcanized rubber, and have moldability not found in vulcanized rubber, they have come to form a field of materials as thermoplastic elastomers. In particular, polyolefin-based thermoplastic elastomers are different from those obtained by block copolymerizing hard segments and soft segments like other polystyrene-based and polyester-based elastomers. , Poly(ethylene-vinyl acetate, etc.) and polyolefin rubber as a soft segment are melt-kneaded, and in some cases, the rubber portion is partially cross-linked during melt-kneading.
As seen in Japanese Patent Publication No. 8 and Japanese Patent Publication No. 53-34210, ethylene-propylene rubber/polypropylene-based rubbers have been put to practical use.

However, these materials require an additional process of melting and mixing the two components, and this significantly increases the cost, which is hindering the expansion of demand. In view of the characteristics they should have, there are quality problems due to the fact that the molecular design of these two parts has not been sufficiently studied up to now.

In particular, conventional products have a good balance between flexibility, strength, and moldability, and in the case of partially crosslinked thermoplastic elastomers, a balance between heat resistance, resistance to permanent distortion, and moldability. That said, it was difficult.

(II) Summary of the Invention The present invention aims to solve these drawbacks of conventional polyolefin thermoplastic elastomers, and provides a crosslinked product derived from a copolymer with specific composition and physical properties. The aim is to achieve this goal by doing so.

Therefore, the crosslinked product of the olefin block copolymer according to the present invention has the following block (A) and block (B).
(However, block (A): block (B) - 5 or more and less than 50 parts by weight: 5
0 and 95 parts by weight or less), and is defined by (1) and (2) below.

Block (A) (a) Homopolymer block of propylene, (b) Binary random copolymer block of propylene and ethylene, and (c) Binary random copolymer block of propylene and α4-12 olefin of C. Block (B) A ternary random copolymer of ethylene, an α-olefin of C, and bropylene containing 75 to 100% by weight of propylene, and having an ethylene content of 30% by weight. % but not more than 85% by weight, and the C α-olefin/propylene weight ratio is 4 to 121 or more.

(1) Content of thermal xylene insoluble fraction is 5-7Sf
The amount of fi should be %.

(2) The fluidity (amount of resin flowing out from the orifice per second [cc/second XIO-3)] measured under the following conditions using a Koka type flow tester is 3 to 200.

Cylinder diameter 10mmφ Orifice diameter 1mlφ Orifice height 2mm Load 30kg Resin temperature 200℃ Effects The copolymer containing the above blocks (A) and (B) has an Olzen bending rigidity (10° angle) of 2 when not crosslinked.
Flexibility of less than 0 0 0 kg/c and 50 kg/c
It has a tensile strength of 1 or more (measurement method described below), and when partially crosslinked, in addition to the flexibility and strength mentioned above, it has a heat-pressure deformation rate (
It exhibits physical properties of heat resistance of 20% or less and permanent deformation of 35% or less (measurement method (described later)).

1> Composition The crosslinked product according to the present invention comprises (a) a propylene homopolymer block, (c) a binary random copolymer block of propylene and ethylene, and (c) a propylene and C
A block (A) selected from 4 to 12 binary random copolymer blocks with an α-olefin of
and one or more of ethylene, α-
Terpolymer block of olefin and propylene (B
) is derived from a block copolymer containing one or more of the following.

This block copolymer from which the crosslinked product according to the present invention is derived does not contain only one block each of (A) and (B), but may contain a plurality of blocks of either one or both. Furthermore, there are no restrictions on how each block is arranged. Also, blocks (A) and (B) are the total 5
Other blocks may coexist as long as they occupy 0flItil% or more.

Block (A) refers to a portion produced by homopolymerization of propylene, or by polymerization in the simultaneous presence of propylene and ethylene or a C 4 -12-olefin. Block (B) refers to a portion produced by polymerization in the simultaneous presence of ethylene, C 2 α-olefin, and 4 to 1 2 propylene. Either (A) or (B) may be formed first. When a plurality of (A) or (and) (B) blocks are included, the individual (A) blocks or (B) blocks do not necessarily have to have the same composition or molecular weight.

Such a block copolymer is produced by polymerizing the necessary monomers in stages to form each block in sequence (details will be described later). By using such a production method, this block copolymer can be produced by having a homopolymer block and a random copolymer block, or a certain set of random copolymer blocks and a random copolymer block having a different composition. Things that coexist in one polymer molecular chain,
a physical mixture of both molecular chains, or a mixture thereof;
It could be one of the following.

This block copolymer from which the crosslinked product of the present invention is derived is:
5 or more but less than 50 parts by weight of one or more blocks (A), preferably 10 or more and less than 50 parts by weight, more preferably 15 or more and less than 50 parts by weight, and 50 parts by weight of one or more blocks (B). more than 95 parts by weight, preferably more than 50 and not more than 90 parts by weight, more preferably more than 50 and not more than 85 parts by weight. Block (A) is a part having characteristics of crystalline thermoplastic resin, and block (A) is a part having characteristics of crystalline thermoplastic resin.
Since B) is a part that has the characteristics of an elastomer with poor quality or low crystallinity, if the content of (A) is below the above range, strength and moldability may decrease, or partial crosslinking may occur as described later. The moldability of the product also becomes poor. On the other hand, if the content of (A) exceeds the above range, flexibility will not be exhibited.

The content of propylene in block (A) is 75 to 10
It is 0% by weight. Since block (A) needs to be a crystalline thermoplastic element, if the propylene content is below the above range, the crystallinity will be too low, which is not preferred. In particular, when propylene is copolymerized with ethylene, the preferred propylene content is 92% by weight or more and less than 95% by weight. When propylene is copolymerized with butene-1, the preferred propylene content is 75% by weight or more and 85! [1
% or less. Further, when propylene is copolymerized with the α-olefin of C, the preferred propylene content is 85% to 92% by weight. Propylene can be homopolymerized or copolymerized with ethylene or C alpha-olefins; monomers that fall into the latter category include butene-1, pentene-1, hexene-1, heptene-1, octene-1 , nonene-1, decene-1, undecene-1 and dodecene-1, as well as 3-methylbutene-1, 3-methylpentene-1, 3-ethylbentene-1, 3-methylhexene-1.
1,4-methylpentene-1, 4.4-dimethylpentene-1, 4-methylhexene-1, 5-methylhexene-1, 5.5-dimethylhexene-1, 3.5-dimethylhexene-1,3, 5. Particular α-olefins such as 5-trimethylhexene-1 are applicable.

Preferred among these comonomers are ethylene, butene-1, hexene-1 and 4-methylpentene-1. Particularly preferred are ethylene, butene-1 or hexene-1.

Block (B) is a ternary random copolymer of ethylene, C4-12 α-olefin, and propylene, but in any case, the ethylene content in block (B) exceeds 30% by weight and is 85% by weight. The amount is preferably 35 to 75% by weight, more preferably 40 to 70% by weight.

Since the block (B) must have elastomeric properties of poor quality or very low crystallinity, if the ethylene content exceeds the above range, the crystallinity will become too high, which is undesirable. On the other hand, if the ethylene content is below the above range, the following problems may occur depending on the type of comonomer used. When the comonomer itself forms a crystalline homopolymer, such as butene-1,4-methylpentene-1, if the ethylene content is below the above range, block (B) is formed.
crystallinity becomes too high. Furthermore, when the comonomer is one that itself forms a liquid homopolymer at room temperature, such as hexene-1, the strength of the block (B) becomes too low.

For the same reason, the ethylene content in the final copolymer from which the crosslinked product of the present invention is derived is more than 15% by weight, preferably 17.5% by weight or more, more preferably 20% by weight or more.
% by weight or more. The upper limit is usually 81% by weight, preferably 70% by weight.

The comonomer is usually selected from α-olefins of 04 to 12, but a part of the content can be replaced by propylene if necessary for the purpose of reducing costs. As a comonomer to be combined with ethylene in block (B), alpha-olefin C is preferable to propylene because it maintains a better balance between strength and flexibility. α of C when considering
- A portion of the olefin, usually less than about half by weight, can be replaced by propylene.

2) The molecular weight of the molecular weight block copolymer is measured by its MFR
(according to ASTM-D-1238 (L)) is 0.01
~200 (g/10 minutes).If it exceeds this, the mechanical properties of the copolymer will not reach a practical level, or the cutting itself will become impossible.MFR lower than this
In this case, the viscoelastic properties in the molten state deteriorate, making it impossible to mold.

3> Fractionation of copolymer The copolymer from which the crosslinked product of the present invention is derived is block (A)
and block (B), and block (A)
is made of a crystalline polymer, and block (B) is made of a rubbery polymer, but the actual situation is as described above, and as a manifestation of the polymolecular nature that polymer compounds inherently have, the mixture is It is.

Therefore, the block copolymer from which the crosslinked product of the present invention is derived can also be defined as having a specific solvent fractionation pattern.

(1) Solvent fractionation Solvent fractionation is performed using cold xylene as follows. That is, 300 ml of p-xylene and approximately 0.
Heat 7g of polymer (Ag) at 160℃ for 5 minutes (
(Using an oil bath) Dissolve the shite, let it cool naturally while immersed in the oil bath, and then leave it at room temperature for 24 hours to precipitate the polymer.

The precipitated polymer is suction filtered through a filter cloth to obtain a solid polymer (Bg after drying) and a solution (Cg after condensation and drying).

Cold xylene solubles (uncorrected) and cold xylene insolubles (uncorrected)
Let cxs' and CXIS' respectively, these are defined as follows.

C:
S and the insoluble fraction CXIS are each defined as follows.

(2) Analysis of fractionation results The cold xylene soluble fraction (CXS) is mainly the rubbery polymer (block (B)) produced in the second stage polymerization (details will be described later). In CXS, melting peaks are generally not observed by DSC (differential scanning calorimetry). The content of CXS is 25%
or more, preferably 35% or more, more preferably 50%
That's it.

On the other hand, the cold xylene insoluble matter (CXIS) is mainly a crystalline polymer (block (A)) produced in the first stage polymerization (details will be described later). CXIS generally has one or more melting peaks observed by DSC, and the temperature of the peak showing the highest temperature is at least 120°C, preferably at least 130°C, more preferably at least 140°C. The content of CXIS is 75% or less, preferably 65% or less, more preferably 50% or less.

2. Production of block copolymer The block copolymer from which the crosslinked product of the present invention is derived is produced by (a) a propylene homopolymer, a random copolymer of propylene and ethylene, or a propylene homopolymer in the presence of a stereoregular polymerization catalyst. and a C4-12 α-olefin in an amount of 5 or more and less than 50 parts 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, and (b) ethylene. , a step of producing more than 50 to 95 parts by weight, preferably more than 50 to 90 parts by weight, more preferably more than 50 to 85 parts by weight, of a ternary random copolymer of C4-12 α-olefin and propylene. It can be manufactured by combining with.

Either of steps (a) and (b) may be carried out first, and other polymerization steps (for example, a propylene homopolymerization step) may be performed before, during, or after (a) and (b). good. (
The polymerization ratio of each monomer in a) and (a) is as described in the section of the composition of the block copolymer.

Suitable stereoregular polymerization catalysts for use in the present invention include, for example, those mainly containing a titanium component and an organoaluminum compound. As the titanium component, a titanium compound supported on a carrier such as α, β, γ, or δ titanium trichloride, magnesium chloride, or the like is used. Among titanium trichlorides, titanium trichloride (the main component is thought to be a eutectic composite of titanium trichloride and aluminum chloride) is obtained by reducing titanium tetrachloride with organoaluminium, and is produced using a complexing agent. When titanium trichloride obtained by extracting and removing aluminum chloride and activated by an appropriate method is used as the titanium component of the catalyst, block (B) can be made more error-prone than when using other titanium trichlorides. Can be made into a stick.

If you want to obtain a high catalyst yield of block copolymer,
It is preferable to use titanium trichloride or titanium tetrachloride supported on magnesium chloride or the like.

The organoaluminum compound has the general formula AIRaY3
It is preferable to use a compound represented by -,. a is Q<a
≦3, Y is a halogen atom, and R is a hydrocarbon residue of approximately 1 to 18 carbon atoms, preferably an alkyl group or an aryl group. Specifically, triethylaluminum, diethylaluminum chloride and the like are preferred.

The catalyst consisting of this combination of two essential components may also be combined with a small amount of an electron donor as a third component. As the electron donor, organic acid esters, polymers, amines, alcohols, ketones, aldehydes, phenols, etc. are used. Specific examples of electron donors that can be used in the present invention can be found in JP-A-54-158489.

Polymerization can be carried out either continuously or batchwise. When carrying out the reaction in a continuous manner, one or more polymerized cypresses are used for each of the steps (a) and (x), and the reaction is carried out under steady conditions in each tank. In the batch method, the next step is started after all or a predetermined amount of the heptanomer in each step has reacted, but once the predetermined amount of monomer has reacted, part or all of the unreacted heptanomer is removed. After taking it out of the tank, the next process will be carried 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 100 kg/cd (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, thereby causing a difference in the molecular weight of the copolymer Pro-Soc produced therein.

Usually, the polymerization is carried out in an inert hydrocarbon such as n-hebutane or n-hexane by a suspension polymerization method or a solution polymerization method.

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. In this crosslinked product, the portion of the copolymer that corresponds to block (B) mainly participates in crosslinking, and the portion corresponding to block (A) hardly participates in crosslinking,
It is thought that this contributes to imparting fluidity to the crosslinked product when it is 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. Moreover, this partially crosslinked structure is the basis for giving this crosslinked product an excellent balance of heat resistance and moldability.

This crosslinked product is partially crosslinked (therefore, it has good heat resistance).
) Excellent moldability and moldability are recognized by gel fraction measured as hot xylene insoluble components and melt flowability under high shear stress measured by a flow tester.

That is, the crosslinked product of the present invention contains a thermally xylene-insoluble component (gel) in an amount of 5 to 75% by weight, preferably 20 to 65% by weight, and more preferably 30 to 60% by weight. When the gel fraction is below the above range, heat resistance is insufficient. Moreover, when the amount exceeds the above range, moldability is impaired.

To measure the thermal xylene gel fraction, use a Soxhlet extractor and set approximately 1 g of a sample cut into as small a size as possible wrapped in an 80-mesh wire mesh.
This is done by extracting for 10 hours under conditions that occur approximately once every minute.

The melt flowability of the crosslinked product of the present invention was determined using a Koka type flow tester under the following conditions.
) is 3 to 200, preferably 4 to 100, more preferably 5 to 80. When the fluidity is below the above range, it becomes difficult to shape the material. Exceeding the above range is not a problem per se, but it is not preferable as a result because it usually accompanies a decrease in gel fraction and impairs heat resistance.

Cylinder diameter 10mmφ Orifice diameter 1 m+sφ Orifice height 2IIl Theoretical load 30kg Resin temperature 200℃ 4. Method for producing a crosslinked product Any known technique can be applied as a method for obtaining a widely crosslinked product.

A typical example is a mechanical melt-kneading method, in which general melt-kneading machines such as a single-screw extruder, a two-screw extruder, a Banbury mixer, and various types of seconders are used, and a known method is used at the melt-kneading stage. Can be partially crosslinked.

As the crosslinking agent, aromatic or aliphatic peroxides or azo compounds are used.

These may be used alone or in combination. Further, in order to obtain a high gel fraction, it is preferable to use a crosslinking aid such as sulfur or a difunctional compound such as a divinyl compound (divinylbenzene, etc.) or a diallyl compound (diallyl phthalate, etc.).

A specific crosslinking agent is 2,5-dimethyl-2,5(
penzoyl peroxy)hexane, 1-butyl peroxyperpenzoate, dicumyl peroxide, 2.5
-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, diisobrobylbenzene hydroperoxide, 1.3-bis-t
-Butylbaroxyisobrobylbenzene, etc.

In crosslinking during mechanical melt mixing, a crosslinking reaction retardant may be used in combination, if necessary, in order to make the crosslinking uniform and control the crosslinking reaction. Such retarders include hydroquinone, 2,6-di-t-butyl-p-cresol, t-butylcatechol, 4,4'-butylidenebis(3-methyl-6-t-butylphenol).
, 2.2'methylenebis(4-methyl-6-t-butylphenol), 4.4'-thiobis(6-t-butyl-3-methylphenol), mercabutobenzothiazole, dibenzothiazole disulfide, 2. 2.
Organic peroxide cross-linked scorch inhibitors such as 4-trimethyl-1,2-dihydroquinone polymer, phenyl-β-naphthylamine, N,N'-di-β-naphthyl-p-furinylene diamine, N-nitrosodiphenylamine, etc. There is.

5. Properties of the copolymer and others as described above, block (A) and block (B)
When uncrosslinked, the copolymer has a flexibility of 2000 kg/cj or less in Olzen bending rigidity (10° angle) and a tensile strength of 50 kg/cd or more (measurement method described later), and when partially crosslinked, In addition to the flexibility and strength mentioned above,
It exhibits physical properties such as heat resistance of 20% or less in terms of heat-pressure deformation rate (measurement method described later) and permanent deformation of 35% or less (791 standard method described later).

This copolymer can be subjected to various modifications and addition of various scavenging materials that are commonly used for polymers. For example, this copolymer is blended with commonly used fillers such as carbon and white pigment, paraffin, naphthenic process oil, plasticizers such as dioctyl phthalate, and pigments, regardless of crosslinking. can do. Further, additives such as a heat stabilizer, an antioxidant, and an ultraviolet absorber can be added as necessary.

6. Large Experimental Examples In the experimental examples below, unless otherwise specified, the test methods used to evaluate each product are as follows.

(1) Melt flow rate (MFR) (230°C, 2.
16kg) ASTM-D-1238 (L) [g/10
min] (2) Olzen bending stiffness (100 squares) ASTM-D-747 [kg/cd] (sample thickness 2
(8) Tensile strength JIS-K-630 1 Test piece No. 3 (kg/cd) (Sample 1 injection molded sheet with a thickness of 2m+s) (4) Tensile elongation JIS-K- 6301 Test piece No. 3 type [%] (5) Fluidity (measure of shapeability) In a Koka flow tester, a sample was placed in a 101II 1-diameter cylinder, heated to 200°C, and then a load of 30 kg was applied to the bottom of the cylinder. II1!1 diameter x 2 installed in
It is obtained by the amount of resin flowing out per second from a vertical orifice. [X 10' CC/sec] (6> Heating and Pressure Deformation Rate A sample (1 cm
A press sheet (x1 cm x 2 mm thick) was attached and left at a temperature of 130°C and a load of 3 kg/cd for one hour, then the load was removed and the thickness deformation rate was obtained after 10 minutes. [%] (7) Permanent elongation (measure of permanent set) JIS-K-6301 test piece No. 1, 100% elongated state, held for 10 minutes, suddenly shrunk, and obtained from the elongation rate after standing for 10 minutes. [%] (8) Gel fraction (content of hot xylene-insoluble components/scale of degree of crosslinking) Approximately 1 g of the sample was wrapped in an 80-mesh stainless steel wire mesh, placed in a Soxhlet extractor, and heated while refluxing hot xylene. After extraction for 10 hours, the ratio of the unextracted portion to the prepared sample is determined. [%] Reference Example 1 After sufficiently purging the inside of a stainless steel reactor with an internal volume of 10 liters equipped with a stirring blade with propylene gas, 4.0% of n-hebutane was added as the polymerization solvent. I put in 0 liters. The internal temperature was set at 60° C., and 0.40 g of diethyl aluminum chloride (DEAC) 2,00+r and titanium trichloride (THL-15, manufactured by Marubeni Solvay Chemical Co., Ltd.) were added as catalysts. Subsequently, propylene and hydrogen were added to 360 ml each.
g/hour and 4.5 liters (in terms of STP)/hour, and both supplies were stopped when the total amount of propylene supplied reached 290 g. While the temperature inside the chamber is 60℃, the pressure inside the chamber is 2. The propylene remaining in the vessel was allowed to react until the pressure decreased to 0 kg/cJ (gauge pressure).

Here, the unreacted gas inside the vessel is reduced to 0. 4kg/c
j (gauge pressure) (block A0
homopolymerization of propylene).

Ethylene and butene-1 were then fed at rates of 75 g/hr and 380 g/hr, respectively, over 30 minutes. During this time, the temperature inside the reactor was maintained at 55° C., and hydrogen was not supplied (hereinafter, block B0 ethylene/butene-1 copolymerization).

The obtained block copolymer was purified with alcohol to obtain a dry product.

Table 1 shows the proportion, composition, and physical properties of each block of the obtained copolymer. However, since it is difficult to calculate the production ratio and composition of each block from only this experiment, the reference example The weight and composition of the polymer obtained by washing, filtering, and drying under the same conditions as above were measured, and the calculations were made indirectly by assuming that these also apply to each polymerization step in the reference example. Further, the composition was determined to be a-1 by carbon 13 NMR.

Reference Example 2 A block copolymer was produced under the same conditions as in Reference Example 1, except that the supply rates of ethylene and butene-1 during block B production were 60 g/hour and 4BOg/hour, respectively.

The results are shown in Table 1.

Reference Comparative Example 1 - The supply rates of ethylene and butene-1 during block B production were 20 g/hour and 480 g/hour, respectively, and 4
, Reference example 1 except that it was fed for O time.
A block copolymer was produced under the same conditions.

The results are shown in Table 1.

Reference Example 3 The amount of n-heptane supplied as a polymerization solvent was 2.6 liters, the temperature of the reactor was 65°C for the production of block B, and ethylene and hexene-1 were used as heptamers instead of ethylene and butene-1. and their feeding rates were set at 70
Block copolymerization was carried out under the same conditions as in Reference Example 1, except that ethylene was supplied for 3 hours and hexene-1 was supplied for 1 hour.

The results are shown in Table 1.

Reference Comparative Example 2 The supply amount of n-hebutane as a polymerization solvent was 3.0 liters, and the total supply amount of propylene and hydrogen supply rate during block A production were 200 g and 5.0 liters, respectively.
STP equivalent)/hour, and the feed rate of ethylene and hexene-1 during block B production was 7
A block copolymer was produced in the same manner as in Reference Example 3, except that the amounts were 5 g/hour and 300 g/hour.

The results are shown in Table 1.

Reference Example 4 During the production of block B, ethylene, butene-1 and propylene were used as monomers at 40 g/hour and 80 g/hour, respectively.
A block copolymer was produced under the same conditions as in Reference Example 1 except that the mixture was fed at a rate of 80 g/hour over 4.0 hours.

The results are shown in Table 1.

Reference Comparative Example 3 The supply rates of propylene and hydrogen during the production of Block A were 90 g/hour and 0.4 liters (STP conversion)/hour, respectively, the total amount of propylene supplied was 15 g, and immediately 0.4 liters of propylene was supplied. 4 kg/cj (gauge pressure) and 2 liters of hydrogen (S
Ethylene, butene-1
A block copolymer was produced under the same conditions as in Reference Example 4, except that the supply time of propylene and hydrogen was 2 hours.

The results are shown in Table 1.

Reference Comparative Example 4 During the production of Block A, the propylene and hydrogen supply rates were respectively 360 g/hour and 2.0 liters (STP conversion)/hour, the total propylene supply amount was 485 g, and 2. After continuing polymerization to 0 kg/cj (gauge pressure), 0. A block copolymer was produced under the same conditions as in Reference Comparative Example 3, except that purging was performed to 4 kg/cJ (gauge pressure) and hydrogen was not supplied during the production of block B.

The results are shown in Table 1.

Reference Example 5 Block B was produced by using ethylene, hexene-1 and propylene as monomers instead of ethylene and hexene-1, and supplying them at a rate of 50 g/hour and 45 g/hour, respectively.
A block copolymer was produced under the same conditions as in Reference Example 3, except that ethylene and propylene were supplied for 3.5 hours and hexene-1 was supplied for 1 hour at 0 g/hour and 100 g/hour.

Reference Comparative Examples When manufacturing block B, butene-1 was not supplied, and ethylene, propylene, and hydrogen were supplied at 40 g/hour and 80 g/hour, respectively.
A block copolymer was produced under the same conditions as in Reference Example 1, except that the mixture was supplied at a rate of 1.0 liters/hour and 1.0 liters/hour (in terms of STP) for 4 hours.

The results are shown in Table 1.

Reference Comparative Example 6 The total amount of propylene supplied during the production of Block A was 90g, and the hydrogen supply rate was 4.0 liters (STP conversion)/hour, and the supply rate was immediately reduced to 0. It was confirmed that hydrogen was purged to 4 kg/cd (gauge pressure) and that 1. Ethylene,
A block copolymer was produced under the same conditions as in Reference Comparative Example 5, except that the propylene and hydrogen supply time was 2 hours and 10 minutes.

The results are shown in Table 1.

Reference Example 6 After the interior of the same reactor as in Reference Example 1 was sufficiently replaced with propylene, 4.0 liters of n-hebutane was added as a polymerization solvent. The internal temperature was set at 55°C, and DEAC2 was used as a catalyst.
．． Og and titanium trichloride (TH manufactured by Marubeni Solvay Chemical Co., Ltd.)
L-15) 0.40g was added. followed by propylene,
21.6 when 360gl each of ethylene and hydrogen
g/h and 5.5 liters (STP equivalent)/h over a period of 50 minutes. After stopping the supply, reduce the pressure inside the vessel to 0.
．． It was discharged until the pressure reached 4 kg/cj (gauge pressure) (block A0 propylene/ethylene copolymerization).

Ethylene and Putene-1 were then fed at a rate of 60 g/hour and 480 g/hour, respectively, over a period of 3 hours and 20 minutes while keeping the temperature inside the vessel at 55°C.

Benio, hydrogen was not supplied during this time (block B
0 ethylene/butene-1 copolymerization).

The obtained block copolymer was purified with alcohol to obtain a dry product.

The results are shown in Table 1.

Reference Example 7 The amount of n-hebutane supplied as a polymerization solvent was 2.6 liters, the temperature of the reactor was 65°C for the production of block B, and ethylene and hexene-1 were used as monomers instead of ethylene and butene-1. A block copolymer was produced under the same conditions as in Reference Example 6, except that the feed rates were 70 g/hour and 900 sr/hour, respectively, and that ethylene was fed for 3 hours and hexene was fed for 1 hour.

The results are shown in Table 1.

Reference Example 8 Block A was manufactured in two stages, firstly propylene was supplied, and after 15 minutes, ethylene was further supplied at a rate of 23.4 g/hour. Not only ethylene and butene-1 but also propylene are supplied, and their supply rates are set at 40% each.
A block copolymer was produced under the same conditions as in Reference Example 6, except that the amounts were 80 g/hour, 80 g/hour, and 80 g/hour.

The results are shown in Table 1.

Reference Example 9 Block A was manufactured by using propylene and putene-1 as monomers instead of propylene and ethylene, and supplying the monomers and hydrogen at a rate of 360 g/hour, respectively.
Block copolymer production was carried out under the same conditions as in Reference Example 8, except that the amount was 150 g/hour and 4.5 liters (STP equivalent)/hour.

The results are shown in Table 1.

Reference Comparative Example 7 The supply rates of propylene and butene water cables during the production of Block A were 120 g/hour, 360 g/hour, and 3.5, respectively.
Block copolymerization was produced under the same conditions as in Reference Example 9, except that the flow rate was liter (STP equivalent)/hour and the supply was carried out for 50 minutes.

The results are shown in Table 1.

Reference Example 10 When producing block B, hexene-1 was used instead of butene-1, and ethylene, propylene, and hexene-1
The feed rates of ethylene and propylene were 50 g/hour, 100 g/hour and 450 g/hour, respectively, and 3.
A block copolymer was produced under the same conditions as in Reference Example 8 except that hexene was supplied for 5 hours and hexene was supplied for 10 hours.

The results are shown in Table 1.

Examples 1 to 10 A pressurized kneader for rubber with a capacity of 1 liter was set at 170°C, 100 parts by weight of each of the copolymers of Reference Examples 1 to 10 was charged, and after melt-kneading for 3 minutes, carbon dioxide was added as a crosslinking agent. Added 0.5 parts by weight of an oxide (Barriki Dox 14J manufactured by Kayaku Nouri Co., Ltd.) and 0.05 parts by weight of dibenzothiazole disulfide as a crosslinking reaction retardant, and melt-kneaded for an additional 7 minutes to obtain each copolymer. A crosslinking treatment was performed.

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

Comparative Examples 1 to 5 Crosslinking treatment was performed under the same conditions as in Example 1 except that the copolymers of Reference Comparative Examples 1 to 4 and 7 were used as raw materials.

Table 2 shows the physical property evaluation results.

Examples 11 to 14 A pressure kneader for rubber with a volume of 1 liter of ffi was set at 170°C, 90 parts by weight of each of the copolymers of Reference Examples 1, 4, 5 and 6 were charged, and after melt-kneading for 3 minutes, Peroxide as a crosslinking agent (Perkadox 14J manufactured by Kayaku Nuri Co., Ltd.)
0.5 parts by weight, liquid 1,2-polybutadiene as a crosslinking aid (rNlsso PB B-3000 manufactured by Nippon Soda Co., Ltd.
J) 10 parts by weight and 0.05 parts by weight of dibenzothiazole disulfide as a crosslinking reaction retardant,
The mixture was melt-kneaded for an additional 7 minutes to crosslink each copolymer.

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

Comparative Example 6 Crosslinking treatment was carried out under the same conditions as in Example 11, except that each copolymer of Reference Comparative Example 1 was used as the raw material copolymer.

Table 2 shows the physical property evaluation results.

Examples 15 to 18 The amount of raw material copolymer (each copolymer of Reference Examples 1, 4, 5, and 6) was 95 parts by weight, and liquid 1 was used as a crosslinking aid.
．． Instead of 2-polybutadiene, use p,p'-dibenzoylquinone dioxime (“Actor DQ” manufactured by Kawaguchi Chemical Industry Co., Ltd.).
J) Crosslinking treatment was carried out under the same conditions as in Example 11 except that 5 parts by weight was added.

The results are shown in Table 2.

Comparative Example 7 Crosslinking treatment was carried out under the same conditions as in Example 15, except that each copolymer of Reference Comparative Example 1 was used as the raw material copolymer.

The results are shown in Table 2.

Claims (1)

[Scope of Claims] An olefinic block copolymer containing the following block (A) and block (B) (however, block (A):
Block (B) = 5 or more and less than 50 parts by weight: more than 50 and 9
5 parts by weight or less) and is defined by (1) and (2) below. Block (A) (a) Homopolymer block of propylene, (b) Binary random copolymer block of propylene and ethylene, and (c) Binary random copolymer of propylene and α-olefin of C_4_ to_1_2. Block (B) is a ternary random copolymer of ethylene, α-olefin of C_4_ to_1_2, and propylene, and has an ethylene content of 30% by weight. exceeding 85% by weight, C_4_
A block in which the α-olefin/propylene weight ratio of ~_1_2 is 1 or more. (1) Content of thermal xylene insoluble components is 5 to 75% by weight
To be. (2) The fluidity (amount of resin flowing out from the orifice per second [cc/sec x 10^-^3]) measured under the following conditions using a Koka type flow tester is 3 to 200. Cylinder diameter 10mmφ Orifice diameter 1mmφ Orifice height 2mm Load 30kg Resin temperature 200℃