JPH0441704B2 - - Google Patents

Description

[Detailed description of the invention]

[] BACKGROUND OF THE INVENTION The present invention relates to a method for producing a partially crosslinked product which is derived from an olefinic block copolymer which has an excellent balance of flexibility, strength and processability, and which has excellent heat resistance and setability. In recent years, expectations for soft materials with excellent heat resistance (particularly shape retention against external forces at high temperatures) and strength have been increasing for automobile parts, household 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 also 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 copolymerization of 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, and in some cases, the rubber part was partially crosslinked during melt-kneading.
As seen in Japanese Patent Publication No. 53938 and Japanese Patent Publication No. 53-34210, ethylene propylene rubber/popypropylene rubber has been put to practical use. However, these materials require an additional process of melting and kneading the two components, and this significantly increases costs, which is a hindrance to expanding demand. In view of the desired characteristics, the molecular design of both components has not been sufficiently studied until now, resulting in quality problems. 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. [] Summary of the Invention The present invention aims to solve these drawbacks of conventional polyolefin thermoplastic elastomers, and involves the production of crosslinked products derived from copolymers with specific compositions and physical properties. It seeks to achieve this objective by providing legislation. Therefore, the method for producing a crosslinked olefinic block copolymer according to the present invention comprises (a) a homopolymer block of propylene, a binary random copolymer of propylene and ethylene, in the presence of a stereoregular polymerization catalyst; _When propylene is copolymerized with ethylene, the propylene content is 92% by weight or more and less than 95% by weight,
When propylene is copolymerized with butene-1, the propylene content is 75% to 85% by weight, and when propylene is copolymerized with _C5-12 α-olefin, the propylene content is 85% to 92% by weight. A step of producing 5 parts by weight or more and less than 50 parts by weight of block (A), and (b) an ethylene content exceeding 30% by weight.
85% by weight or less, C _4-12 α-olefin/
Ethylene with a weight ratio of propylene of 1 or more
An olefin system obtained by combining with a step of producing more than 50 parts by weight and less than 95 parts by weight of block (B), which is a ternary random copolymer block of C _{4 to 12} α-olefin and propylene. When the block copolymer is crosslinked, (1) the content of the hot xylene insoluble component is 5 to 75% by weight; (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. The present invention is characterized by obtaining a crosslinked olefin block copolymer having the following characteristics: cylinder diameter: 10 mmφ, orifice diameter: 1 mmφ, orifice height: 2 mm, load: 30 kg, and resin temperature: 200°C. Effect The copolymer containing the above blocks (A) and (B) has a high Olzen bending rigidity (10° angle) when not crosslinked.
It has a flexibility of 2000 kg/cm ² or less and a tensile strength of 50 kg/cm ² or more (measurement method described later), and when partially crosslinked, in addition to the flexibility and strength mentioned above, it has a heat-pressure deformation rate (measurement method It exhibits physical properties such as heat resistance of 20% or less and permanent deformation of 35% or less (measurement method described below). [] Detailed Description of the Invention 1 Block Copolymer (1) Composition The crosslinked product according to the present invention comprises (a) a propylene homopolymer block, (b) a binary random copolymer block of propylene and ethylene, and ( c)
One or more blocks (A) selected from binary random copolymer blocks of propylene and a C _4-12 α-olefin, and a ternary copolymer block of ethylene, a C _4-12 α-olefin, and propylene. It is derived from a block copolymer containing one or more of the copolymer blocks (B). In the present invention, this block copolymer from which a crosslinked product is derived does not contain only one block each of (A) and (B), but may contain a plurality of either or both blocks. Furthermore, there are no restrictions on how each block is arranged.
In addition, blocks (A) and (B) account for 50% of the total weight.
Other blocks may coexist as long as they occupy the above number. Block (A) is produced by homopolymerization of propylene, or by polymerization of propylene and ethylene or
It refers to the part produced by polymerization in the presence of a _C4-12 α-olefin. Block (B) is ethylene, _C4-12 α-
It refers to the part produced by polymerization under conditions where olefin and propylene are present simultaneously. Either (A) or (B) may be formed first. If multiple (A) or (and) (B) blocks are included, each (A) block or (B)
The blocks do not necessarily have to have the same composition or molecular weight. Such block copolymers are produced by stepwise polymerization of the required monomers to form each block in sequence (details below). By using such a production method, this block copolymer can be produced by combining a homopolymer block and a random copolymer block, or a random copolymer block having a certain composition and a random copolymer block having a different composition. It may coexist with the actual polymer molecular chain, be a physical mixture of both molecular chains, or be a mixture thereof. This block copolymer from which the crosslinked product of the invention is derived may contain one or more blocks.
5 or more and less than 50 parts by weight of (A), preferably 10 or more
Less than 50 parts by weight, more preferably 15 or more and less than 50 parts by weight, and one or more blocks (B)
more than 50 and less than 95 parts by weight, preferably more than 50 and less than 90 parts by weight, more preferably more than 50 and less than 85 parts by weight.
Including parts by weight or less. Since the block (A) is a part that has the characteristics of a crystalline thermoplastic resin, and the block (B) is a part that has the characteristics of an amorphous or low-crystalline elastomer, the content of (A) is within the above range. If the temperature is lower than that, the strength and moldability will decrease, and as will be described later, the moldability of partially crosslinked products will also be 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
~100% by weight. Since the block (A) must be a crystalline thermoplastic element, if the propylene content is below the above range, the crystallinity will be too low, which is undesirable. In particular, when propylene is copolymerized with ethylene, the preferred propylene content is 92% by weight or more and less than 95% by weight. The preferred propylene content when copolymerizing propylene with butene-1 is
It is 75% by weight or more and 85% by weight or less. Further, when propylene is copolymerized with a _C5-12 α-olefin, the preferred propylene content is 85% by weight or more and 92% by weight or less. Propylene can be homopolymerized or copolymerized with ethylene or _C4-12 alpha-olefins, but monomers that fall into the latter comonomer category include butene,
1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1
1, linear α-olefins such as undecene-1 and dodecene-1, and 3-methylbutene-1, 3-methylpentene-1, 3-ethylpentene-1, 3-methylhexene-
1,4-methylpentene-1,4,4-dimethylpentene-1,4-methylhexene-
1,5-Methylhexene-1,5,5-dimethylhexene-1,3,5-dimethylhexene-1,3,5,5-trimethylhexene-
This applies to branched α-olefins of the order of 1. 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. % or less, preferably 37 to 75% by weight, more preferably 40 to 70% by weight. Block (B) needs to have amorphous or extremely low crystallinity elastomer properties.
If the ethylene content exceeds the above range, the crystallinity will become too high, which is not preferable. 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. The comonomer is butene-1,4-
In the case of methylpentene-1 which itself can form a crystalline homopolymer, if the ethylene content is below the above range, the crystallinity of block (B) will become too high. In addition, if the comonomer is one that itself forms a liquid homopolymer at room temperature, such as hexene-1, the block
The strength of (B) becomes too low. For similar reasons, 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. The upper limit is usually 81% by weight, preferably 70% by weight. The comonomer is usually selected from among _C4-12 α-olefins, but a part of the content can be replaced by propylene if necessary for cost reduction purposes. block
As a comonomer to be combined with ethylene in (B), _C4-12 α-olefin is preferable to propylene because it maintains a better balance between strength and flexibility, but the balance should also be considered in consideration of cost. In some cases, a portion of the C _4-12 α-olefin, typically less than about half on a weight basis, can be replaced with propylene. (2) Molecular weight The molecular weight of block copolymers is determined by the MFR (according to ASTM-D-1238(L)), which is a measure of the molecular weight of block copolymers.
It needs to be 0.01 to 200 [g/10 minutes].
If it exceeds this range, the mechanical properties of the copolymer will not reach a practical level, or molding itself will become impossible. If the MFR is lower than this, the viscoelastic properties in the molten state deteriorate and molding becomes impossible. (3) Fractionation of copolymer The copolymer from which the crosslinked product of the present invention is derived contains block (A) and block (B),
Block (A) is made from a crystalline polymer, block (B)
are made of rubbery polymers, but in reality, as mentioned above, and as a manifestation of the polymolecular nature that polymer compounds inherently have, they are mixtures. 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, p-xylene
Approximately 0.7 g of polymer (A
g) for 15 minutes at 160°C (using an oil bath) to dissolve it, 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 concentration and drying). Cold xylene solubles (uncorrected) and xylene insolubles (uncorrected) were measured by CXS′ and
CXIS′, these are defined as follows. CXS' = C/A x 100 (weight%) CXIS' = B/A x 100 (weight%) Usually some loss occurs, and CXS'+
Since CXIS′ < 100, the cold xylene soluble portion CXS and the same insoluble portion CXIS are corrected.
are defined as follows. CXS = CXS' / CXS' + CXIS' × 100 (weight%) CXIS = CXIS' / CXS' + CXIS' × 100 (weight%) (2) Analysis of fractionation results Cold xylene soluble fraction (CXS) is mainly This is a rubbery polymer (block (B)) produced through two-stage polymerization (details described later). CXS is
Generally, no melting peak is observed by DSC (differential scanning calorimeter). The content of CXS is
It is 25% or more, preferably 35% or more, and more preferably 50% or more. On the other hand, cold xylene insoluble matter (CXIS) is
It is mainly a crystalline polymer (block (A)) produced in the first stage of 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 below 75%, 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 homopolymer of propylene, a random copolymer of propylene and ethylene, or 5 or more random copolymers of propylene and _C4-12 α-olefins
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 _. It can be produced by combining with 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. Either of steps (a) and (b) may be performed first,
Furthermore, other polymerization steps (for example, a propylene homopolymerization step) may be included before, during, or after (a) and (b). The polymerization ratio of each monomer in (a) and (b) 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, the block (B) becomes more elastic than when using other titanium trichlorides. It can be done. When it is desired to obtain a high catalyst-based yield of the block copolymer, it is preferable to use titanium trichloride or titanium tetrachloride supported on magnesium chloride or the like. As an organoaluminum compound, the general formula
It is preferable to use a compound represented by A1RaY _3-a . a is any number of 0<a≦3, Y is a halogen atom, R is a hydrocarbon residue of about C _{1 to 18} ,
Preferred are alkyl groups and aryl groups. Specifically, triethylaluminum, diethylaluminum chloride and the like are preferred. Catalysts consisting of this combination of two essential components include:
A small amount of an electron donor may be combined as a third component. Examples of electron donors include organic acid esters, ethers, amines, alcohols, ketones,
Aldehydes, phenols, etc. are used. Specific examples of electron donors that can be used in the present invention are
54-158489. Polymerization can be carried out either continuously or batchwise. When conducting in a continuous manner, one or more polymerization tanks are used for each of the steps (a) and (b), 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 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. After it is released, the next process will be carried out. In the method of the present invention, the polymerization temperature is usually 0 to 200°C;
The polymerization pressure is carried out in the range of 0 to 100 Kg/cm ² (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 resulting copolymer blocks. Usually, polymerization is carried out in an inert hydrocarbon such as n-heptane or n-hexane using a suspension polymerization method or a solution gravimetric 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 two sections.
In this crosslinked product, the part corresponding to block (B) of the copolymer mainly participates in crosslinking, and the part corresponding to block (A) hardly participates in crosslinking, giving fluidity to the crosslinked product when melted. It is thought that this contributes to the 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. This partially crosslinked structure is also the basis for giving the crosslinked product an excellent balance of heat resistance and moldability. The fact that this crosslinked product is partially crosslinked (therefore has good heat resistance) and excellent moldability is due to the gel fraction measured as a hot xylene insoluble component and the high shear stress measured with a flow tester. It is recognized by its melt flowability. That is, the crosslinked product of the present invention contains 5 to 75% by weight of the hot xylene insoluble component (gel), preferably 20% by weight.
It contains up to 65% by weight, more preferably 30 to 60% by weight. If the gel fraction is below the above range,
Heat resistance is insufficient. Moreover, when the amount exceeds the above range, moldability is impaired. Thermal xylene gel fraction was measured by using a Soxhlet extractor and placing approximately 1 g of the sample cut into small pieces wrapped in an 80-mesh wire mesh under conditions where p-xylene reflux occurred approximately once every 30 minutes. This is done by extracting for 10 hours. The melt flowability of the crosslinked product of the present invention was measured using a Koka type flow tester under ^the following conditions. , preferably 4~
It needs to be 100, more preferably 5-80. If the fluidity falls below the previous range, molding becomes difficult. 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: 1mmφ Orifice height: 2mm Load: 30Kg Resin temperature: 200°C 4. Method for producing crosslinked product Any known technique can be applied as a method for obtaining the crosslinked product. A typical example is the mechanical melt-kneading method,
Partial crosslinking can be carried out by a known method during the melt-kneading stage using a general melt-kneader such as a single-screw extruder, twin-screw extruder, Banbury mixer, or various kneaders. As the crosslinking agent, aromatic or resinous 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.). Specific crosslinking agents include 2,5-dimethyl-2,5(benzoylperoxy)hexane,
t-Butyl peroxyperbenzoate, dicumyl peroxide, 2,5-dimethyl-2,
5-di(t-butylperoxy)hexane, t
-Butylcumyl peroxide, diisopropylbenzene hydroperoxide, 1,3-
Examples include bis-t-butylperoxyisopropylbenzene. In crosslinking during mechanical melt-kneading, 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), mercaptobenzothiazole, dibenzothiazole disulfide, 2,2,4-trimethyl-
1,2-dihydroquinone polymer, phenyl-
There are organic peroxide crosslinking scorch inhibitors such as β-naphthylamine, N,N'-di-β-naphthyl-p-phenylenediamine, and N-nitrosodiphenylamine. 5 Properties of copolymer and others As mentioned above, the above block (A) and block
The copolymer containing (B) has a flexibility of less than 2000 Kg/cm ² in Olzen bending rigidity (10° angle) and a tensile strength of 50 Kg/cm ² or more (measurement method described later) when non-crosslinked.
When partially crosslinked, in addition to the flexibility and strength mentioned above, the deformation rate under heat and pressure (measurement method described later)
Demonstrates physical properties of heat resistance of 20% or less and permanent deformation of 35% or less (measurement method described below). This copolymer can be subjected to various modifications and addition of various auxiliary materials that are commonly used for polymers. For example, this copolymer is blended with commonly used carbon, fillers such as white pigments, paraffins, naphthenic process oils, 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 Experimental Examples In the experimental examples below, unless otherwise indicated,
The test methods used to evaluate each product are as follows. (1) Melt flow rate (MFR) (230℃,
2.16Kg) ASTM-D-1238(L) [g/10 minutes] (2) Olzen bending stiffness (10° angle) ASTM-D-747 [Kg/cm ² ] (Sample = 2mm thick press sheet) ( 3) Tensile strength JIS-K-6301 test piece No. 3 type [Kg/cm ² ] (Sample = 2 mm thick injection molded sheet) (4) Tensile elongation JIS-K-6301 test piece No. 3 type [%] (5) Fluidity (measure of formability) In a Koka type flow tester, a sample was placed in a 10 mm diameter cylinder, heated to 200℃, and then
It is obtained by applying a load of Kg to the amount of resin flowing out per second from an orifice with a diameter of 1 mm and a height of 2 mm provided at the bottom of the cylinder. [×10 ^-3
cc/sec] (6) Heat-pressure deformation rate A sample (1 cm x 1 cm x 2 mm thick press sheet) was measured using a device capable of applying a load to the sample in heated silicone oil and measuring the deformation of the sample. attached, temperature 130℃, load 3
After being left at Kg/cm ² for one hour, the load is removed and the thickness deformation rate is obtained after 10 minutes. [%] (7) Permanent Elongation (Measure of Permanent Set) JIS-K-6301 Test Piece No. 1 100% elongated state is held for 10 minutes, then suddenly shrunk and left for 10 minutes. Obtained from the elongation rate. [%] (8) Gel fraction (content of hot xylene-insoluble components/scale of degree of crosslinking) Wrap 1 g of sample in an 80-mesh stainless steel wire mesh, place it in a Soxhlet extractor, and heat xylene under reflux for 10 minutes. After extraction over a period of time, the proportion of the unextracted portion to the prepared sample is determined. [%] Reference Example 1 After the inside of a stainless steel reactor equipped with a stirring blade and having an internal volume of 10 liters was sufficiently replaced with propylene gas, 4.0 liters of n-heptane was added as a polymerization solvent. Set the internal temperature to 60℃ and use 2.00g of diethylaluminum chloride (DEAC) as a catalyst.
and titanium trichloride (manufactured by Marubeni Solvay Chemical Co., Ltd.)
THL-15) 0.40g was added. Subsequently, propylene and hydrogen were supplied at a rate of 360 g/hour and 4.5 liters (STP equivalent)/hour, respectively, and when the total amount of propylene supplied reached 290 g, the supply of both was stopped. The propylene remaining in the vessel was allowed to react while the temperature in the vessel was kept at 60°C until the pressure in the vessel decreased to 2.0 Kg/cm ² (gauge pressure). Here, the unreacted gas in the vessel was released until the pressure in the vessel reached 0.4 Kg/cm ² (gauge pressure) (block A. Homopolymerization of propylene). Next, ethylene and butene-1 were each added at 75%
g/hr and 380 g/hr over a period of 3 hours and 30 minutes. During this time, the temperature inside the reactor was maintained at 55°C and hydrogen was not supplied (block B above).
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 phase. However, it is difficult to calculate the production ratio and composition of each block from this experiment alone, so we performed the intermediate polymerization stage separately under the same conditions as in the reference example above, and then immediately decomposed the catalyst. Washed, filtered and separated under the same conditions.
This was indirectly calculated by measuring the weight and composition of the polymer obtained by drying and assuming that these also apply to each polymerization step in the reference example. Moreover, the composition was measured by carbon 13 NMR. Reference example 2 Ethylene and butene-1 during production of block B
A block copolymer was produced under the same conditions as in Reference Example 1, except that the feed rates were 60 g/hour and 480 g/hour, respectively. The results are shown in Table 1. Reference comparative example 1 Ethylene and butene-1 during production of block B
A block copolymer was produced under the same conditions as in Reference Example 1, except that the feeding rates were 20 g/hour and 480 g/hour, respectively, and the feeding was continued for 4.0 hours. 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 monomers instead of ethylene and butene-1. Block copolymerization was carried out under the same conditions as in Reference Example 1, except that the feeding rates were 70 g/hour and 900 g/hour, respectively, and ethylene was fed for 3 hours and hexene-1 was fed for 1 hour. . The results are shown in Table 1. Reference Comparative Example 2 The supply amount of n-heptane 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 200 g, respectively.
5.0 liters (STP equivalent)/hour, and ethylene and hexene during block B production.
1 feed rate of 75 g/hour and 300 g/hour, respectively.
A block copolymer was produced in the same manner as in Reference Example 3 except for the following. The results are shown in Table 1. Reference example 4 When manufacturing block B, 40% each of ethylene, butene-1 and propylene were used as monomers.
A block copolymer was produced under the same conditions as in Reference Example 1, except that it was fed at a rate of 80 g/hour, 80 g/hour, and 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, and the total amount of propylene supplied was
15g, and immediately purged to 0.4Kg/cm ² (gauge pressure), and when manufacturing block B, hydrogen was supplied at a rate of 2 liters (STP conversion)/hour.
A block copolymer was produced under the same conditions as in Reference Example 4, except that the supply time of ethylene, butene-1, propylene, and hydrogen was 2 hours. The results are shown in Table 1. Reference comparative example 4 Propylene and hydrogen supply rates during block A production were 360 g/hour and 2.0 liters (STP conversion)/hour, respectively, and the total propylene supply amount was 485 g/hour.
g, and continued polymerization to 2.0 g/cm ² (gauge pressure), and then purged to 0.4 kg/cm ² (gauge pressure), and hydrogen was not supplied during the production of block B. A block copolymer was produced under the same conditions as in Reference Comparative Example 3 except for this. The results are shown in Table 1. Reference Example 5 Block B was produced using ethylene, hexene-1 and propylene as monomers instead of ethylene and hexene-1, and their feed rates were 50 g/hour, 450 g/hour and 100 g/hour, respectively.
Ethylene, propylene for 3.5 hours, hexene-1
Reference example 3, except that it was supplied for one hour.
A block copolymer was produced under the same conditions as above. Reference Comparative Example 5 Butene-1 was not supplied during the production of block B,
A block copolymer was produced under the same conditions as in Reference Example 1, except that ethylene, propylene, and hydrogen were supplied over 4 hours at a rate of 40 g/hour, 80 g/hour, and 1.0 liters (STP equivalent)/hour, respectively. did. The results are shown in Table 1. Reference comparative example 6 The total amount of propylene supplied during block A production was 90
g, the hydrogen supply rate is 4.0 liters (STP conversion)/hour, and immediately 0.4Kg/cm ² (gauge pressure)
The same procedure as Reference Comparative Example 5 was performed except that hydrogen was supplied at a rate of 1.0 liters (STP equivalent)/hour during block B production, and the supply time of ethylene, propylene, and hydrogen was 2 hours and 10 minutes. A block copolymer was produced under similar conditions. 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-heptane was added as a polymerization solvent. The internal temperature was set at 55° C., and 2.0 g of DEAC and 0.40 g of titanium trichloride (THL-15, manufactured by Marubeni Solvay Chemical Co., Ltd.) were added as catalysts. Subsequently, propylene, ethylene and hydrogen were fed over a period of 50 minutes at rates of 360 g/h, 21.6 g/h and 5.5 liters (STP equivalent)/h, respectively. After stopping the supply, increase the pressure inside the vessel to 0.4Kg/cm ² (gauge pressure)
(The above is Block A. Propylene/ethylene copolymerization). Ethylene and butene-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. In addition,
During this time, hydrogen was not supplied (above block B. 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-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 monomers instead of ethylene and butene-1. The feeding rates are 70 g/hour and 900 g/hour, respectively.
Block copolymerization was produced under the same conditions as in Reference Example 6, except that ethylene was supplied for 3 hours and hexene was supplied for 1 hour. The results are shown in Table 1. Reference Example 8 The production of block A was carried out in two stages, in which propylene was first supplied, and after 15 minutes, ethylene was further supplied at a rate of 23.4 g/hour. A block copolymer was produced under the same conditions as in Reference Example 6, except that not only butene-1 but also propylene was supplied, and the feeding rates were 40 g/hour, 80 g/hour, and 80 g/hour, respectively. did. The results are shown in Table 1. Reference Example 9 Block A was manufactured using propylene and butene-1 as monomers instead of propylene and ethylene, and the supply rates of these monomers and hydrogen were 360 g/hour, 150 g/hour, and 4.5 liters (STP conversion)/hour, respectively. A block copolymer was produced under the same conditions as in Reference Example 8 except for the above. The results are shown in Table 1. Reference Comparative Example 7 The supply rates of propylene and butene hydrogen during the production of Block A were 120 g/hour, 360 g/hour and 360 g/hour, respectively.
Block copolymerization was produced under the same conditions as in Reference Example 9, except that the flow rate was 3.5 liters (in terms of STP)/hour and the supply was carried out for 50 minutes. The results are shown in Table 1. Reference Example 10 During the production of block B, hexene-1 was used instead of butene-1, and the feeding rate of ethylene, propylene, and hexene-1 was each 50 g/hour.
A block copolymer was produced under the same conditions as in Reference Example 8, except that ethylene and propylene were supplied over 3.5 hours and hexene was supplied over 10 hours at 100 g/hour and 450 g/hour. The results are shown in Table 1. Examples 1 to 10 A pressure kneader for rubber with a capacity of 1 liter was heated to 170℃.
100 parts by weight of each of the copolymers of Reference Examples 1 to 10 were added and melt-kneaded for 3 minutes.
14'') and 0.05 part by weight of dibenzothiazole disulfide as a crosslinking reaction retarder were added and 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 Examples 1 to 5 Crosslinking treatment was carried out 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 11-14 A pressure kneader for rubber with a capacity of 1 liter was heated to 170℃.
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,
0.5 parts by weight of peroxide ("Perkadox 14" manufactured by Kayaku Nouri Co., Ltd.) as a crosslinking agent, 10 parts by weight of liquid 1,2-polybutadiene ("NISSO PB B-3000" manufactured by Nippon Soda Co., Ltd.) as a crosslinking aid, and crosslinking reaction 0.05 parts by weight of dibenzothiazole disulfide was added as a retarder, and the mixture was melt-kneaded for an additional 7 minutes.
Each copolymer was crosslinked. 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 the raw material copolymer (each copolymer of Reference Examples 1, 4, 5, and 6) was 95 parts by weight, and p,
Crosslinking treatment was carried out under the same conditions as in Example 11, except that 5 parts by weight of p'-dibenzoylquinone dioxime ("Actor DQ" manufactured by Kawaguchi Chemical Industry Co., Ltd.) was charged. 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. Comparative Reference Example 8 A block copolymer was produced under the same conditions as in Reference Example 6, except that the supply rates of propylene and ethylene during the production of Block A were 334 g/hour and 46 g/hour, respectively. The results are shown in Table 1. Comparative Example 8 Crosslinking treatment was carried out under the same conditions as in Example 1, except that the copolymer produced in Reference Comparative Example 8 was used as the raw material copolymer. Table 2 shows the physical property evaluation results. Comparative Reference Example 9 A block copolymer was produced under the same conditions as in Reference Example 9, except that the supply rates of propylene and butene during the production of Block A were 300 g/hour and 200 g/hour, respectively. The results are shown in Table 1. Comparative Example 9 Crosslinking treatment was carried out under the same conditions as in Example 1, except that the copolymer produced in Reference Comparative Example 9 was used as the raw material copolymer. Table 2 shows the physical property evaluation results.

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[Table] * Shows data that deviate from the requirements of the present invention.

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FIG. 1 is a flowchart to help understand the technical contents of the present invention regarding Ziegler catalysts.

Claims (1)

[Scope of Claims] 1. In the presence of a stereoregular polymerization catalyst, (a) a propylene homopolymer block, a binary random copolymer block of propylene and ethylene, and propylene and a C _4-12 α-olefin; When propylene is copolymerized with ethylene, the propylene content is 92% by weight.
95% by weight or more, when propylene is copolymerized with butene-1, the propylene content is 75% or more by weight85
If propylene is copolymerized with C _5-12 α-olefin, the propylene content is 85% by weight or less.
A step of producing 5 parts by weight or more and less than 50 parts by weight of block (A) having an ethylene content of more than 30% by weight and less than 85% by weight, and a C _{4 to 12}
More than 50 parts by weight or more than 95 parts by weight of block (B) which is a ternary random copolymer block of ethylene, C _{4 to 12} α-olefin and propylene in which the weight ratio of α-olefin/propylene is 1 or more; The olefinic block copolymer obtained by the following steps is crosslinked, and (1) the content of the thermally xylene-insoluble component is 5 to 75% by weight. (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: 10 mmφ Orifice diameter: 1 mmφ Orifice height: 2 mm Load: 30 Kg Resin temperature: 200°C A method for producing a crosslinked olefin block copolymer, characterized by obtaining a crosslinked olefin block copolymer having the following characteristics. .