JPH01247441A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in heat resistance, tensile strength, weathering resistance and balance between rigidity and impact resistance, etc., by dynamically heat-treating an ethylene/alpha-olefin copolymer rubber and a specified polyolefin resin in the presence of a crosslinking agent. CONSTITUTION:A catalyst (b) is obtained by bringing a highly active titanium solid catalyst component (i) having Mg, Ti and a halogen as essential components, an organometallic compound catalyst component (ii) containing a Group I-III metal of the periodic table and an electrondonating catalyst component (iii) of which at least part may be contained in component (i) into contact with each other in the presence of an alpha-olefin at -50-100 deg.C for 1min-10hr in an inert medium. An alpha-olefin (a) is polymerized at 20-200 deg.C in the presence of component (b) under a normal pressure to 100kg/cm<2> to obtain a polyolefin resin (B). 100 pts.wt. mixture of 100-10 pts.wt. ethylene/alpha-olefin copolymer rubber (A) of a Q value (weight-average MW/number-average MW according to gel permeation chromatography) of 2.5-8 with 0-30 pts.wt. component B is dynamically heat-treated in the presence of a crosslinking agent to obtain the title composition at least partially crosslinked.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic elastomer composition, and more specifically, it has excellent heat resistance, tensile strength, weather resistance, flexibility, and elasticity, as well as rigidity and durability. This invention relates to a thermoplastic elastomer composition with excellent balance of WI impact properties.

Thermoplastic elastomers have been widely used as automobile parts such as 1+ bumper parts and 1+ bumpers.

This thermoplastic elastomer has both thermoplastic and elastic properties, and can be molded into molded products with excellent heat resistance, tensile properties, weather resistance, flexibility, and elasticity by injection molding, extrusion molding, etc. be able to.

As such a thermoplastic elastomer, for example, Japanese Patent Publication No. 53-34210 discloses a method in which 60 to 80 parts by weight of monoolefin copolymer rubber and 40 to 20 parts by weight of polyolefin plastic are dynamically partially cured. A thermoplastic elastomer is disclosed. Also, special public service in 1973
Publication No. 21021 discloses that (a) it is made of ethylene-propylene-nonconjugated polyene copolymer rubber and has a gel content of 3
0 to 90% by weight of a partially crosslinked copolymer rubber; (b)
A thermoplastic elastomer comprising a polyolefin resin is disclosed. Furthermore, Japanese Patent Publication No. 55-18448 discloses a thermoplastic elastomer in which an ethylene-propylene copolymer rubber and a polyolefin resin are dynamically partially or completely crosslinked.

The above thermoplastic elastomer composition can be manufactured by injection molding, extrusion molding, etc. to improve heat resistance, tensile strength, weather resistance,
It can be molded into a molded product with excellent flexibility and elasticity, but if this molded product is to be used, for example, in an automobile bumper, rigidity is required. There was a problem that the quality decreased.

The present inventors have conducted extensive studies to obtain a thermoplastic elastomer composition that does not reduce impact resistance when rigidity is imparted to a thermoplastic elastomer composition that has excellent heat resistance, flexibility, elasticity, etc. discovered that a thermoplastic elastomer obtained by dynamically crosslinking an ethylene/α-olefin copolymer rubber and a specific polyolefin resin had the above-mentioned properties, and completed the present invention. I ended up doing it.

SUMMARY OF THE INVENTION The present invention aims to solve the problems associated with the prior art as described above. It is an object of the present invention to provide a thermoplastic elastomer composition that can provide an excellent molded article whose impact resistance does not deteriorate even when the impact resistance is increased.

lHadatetaka J The first thermoplastic elastomer composition according to the present invention contains (a) ethylene/α-olefin copolymer rubber, and (b) (iii) magnesium, titanium, and halogen as essential components. a highly active titanium solid catalyst component, (11) an organometallic compound catalyst component of a metal from Group 1 to Group 3 of the periodic table, and (iii) an electron donor catalyst component ((iii) is a part or whole of (1) ) A mixture containing as an essential component a polyolefin resin obtained by polymerizing an α-olefin using a catalyst formed from ), which may be contained in a highly active titanium solid catalyst component,
It is characterized by being partially or completely crosslinked by dynamic heat treatment in the presence of a crosslinking agent.

Further, a second thermoplastic elastomer composition according to the present invention is characterized in that a polyolefin is further blended into the thermoplastic elastomer composition as described above.

Since the thermoplastic elastomer composition according to the present invention is composed of the above-mentioned components, it has excellent heat resistance, tensile strength, weather resistance, flexibility, elasticity, etc., and also has impact resistance even when rigidity is not increased. It is possible to provide an excellent molded product with no deterioration in quality.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The thermoplastic elastomer composition according to the present invention will now be described in detail.

The thermoplastic elastomer composition according to the present invention comprises (a) an ethylene/α-olefin copolymer rubber, and fb) a polyolefin resin obtained by polymerizing α-olefin using a specific catalyst. It is cross-linked by heat treatment,
Each component will be explained below.

a) Ethylene/α-Refin Kurekita Shigeima (a) Ethylene/α-olefin copolymer rubber, which is a raw material for rubber thermoplastic elastomers, includes, for example, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated Ethylene and 3 to 14 carbon atoms, such as diene ternary or multicomponent copolymer rubber, ethylene-butadiene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-butene-nonconjugated diene multicompolymer rubber, etc. A substantially amorphous copolymer rubber containing α-olefin as a main component or a mixture thereof. Among these, ethylene-propylene copolymer rubber and ethylene-propylene-nonconjugated diene terpolymer rubber are preferred.

Here, the non-conjugated diene is dicyclopentadiene, 1
．． It means 4-hexadiene, cyclooctadiene, methylenenorbornene, 5-ethylidene-2-norbornene, etc., and in the present invention, among these, ternary one having dicyclopentadiene or 5-ethylidene-2-norbornene as the third component Copolymer or dicyclopentadiene and 5
A quaternary copolymer containing both components -ethylidene-2-norbornene is preferred.

Mooney viscosity [WL
(100°C)] is usually 10 to 180.1°C, preferably 40 to 140, and its iodine value (degree of unsaturation) is preferably 16 or less.

In the present invention, the ratio of each compositional unit contained in these copolymer rubbers is 90/l of ethylene units/α-olefin units in the 1-olefin portion.

~50150, preferably 80/20~60/40 (
molar ratio). 1-olefin (ethylene + α
-Olefin) unit/non-conjugated diene JiL position (in the case of ternary or multi-component copolymers) is usually 98/2 to 90/1
0, preferably 97/3 to 911/6 (molar ratio).

Such (a) ethylene/α-olefin copolymer rubber has a Qfii (weight average molecular weight/number average molecular weight) of 2.5 to 8 as measured by the tal permeation method (GPC method). It is preferable that there be.

By using (a) ethylene/α-olefin copolymer rubber having a Q value of 2.5 to 8, a thermoplastic elastomer composition with an excellent balance between rigidity and street shock resistance can be obtained.

The measurement of Qi is written by Takeuchi, Maru 1! It was carried out as follows according to the published [Gelvermeation Chromatography].

(1) Using standard polystyrene with a known molecular weight (monodispersed polystyrene manufactured by Toyo Soda Co., Ltd.), the molecule ff1M and its G P C (Gel Per + 5eation Ch
rona↑ograph) count and molecular weight M
A correlation diagram calibration curve of E V (Hution Volur #c) is plotted. The concentration at this time is 0.02% by weight.

+2) Obtain a GPC pattern of the sample using the GPC measurement method and find out M using (1) above. Sample preparation conditions and GPC11M! The conditions are as follows.

Sample preparation (a) Add 0-dichlorobenzene to 0.04% by weight of the sample. 8v! , into an Erlenmeyer flask.

(b) Add anti-aging agent to the Erlenmeyer flask containing the sample.
Add 0.1% by weight of 6-sheet tcrt-butyl-p-cresol to the polymer solution.

(c) Heat the Erlenmeyer flask to 140°C and stir for about 30 minutes to dissolve.

(d) Then filter through a 1μ Millipore filter at 135°C to 140°C.

(e) Apply the P solution to GPC.

GPCiTII conditions It was conducted under the following conditions.

(B) Equipment 200 type (B) Column manufactured by Waters Co., Ltd. S-type (Mix type) (C) San'fil ft2a11 (D) Temperature 135°C (E) Flow rate 1ml/ The total number of theoretical plates for Calm is 2X10' to 4X104b. Polyrefine polyolefin resins include ethylene, propylene,
A homopolymer of 1-olefin such as butene-1, hexene-1,4-methyl-1-pentene, a copolymer of two or more thereof, or an α-olefin and 15 mol% or less of other polymerizable monomers. Copolymers with ethylene-vinyl acetate, ethylene-acrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene- Examples include resinous polymeric substances such as methyl methacrylate copolymers. Of these, melt index (
ASTM-D-1238-657) is 0.1 to 80 t
/ 10 minutes (230 ° C), especially 5-20 t / 1
A polyolefin resin having a crystallinity of 40% or more as determined by X-ray diffraction measurement is preferably used.

Among these, preferred polyolefin resin (b) is a melt index of 0.1 to 50 g/10 min (2
30°C) and a crystallinity of 40% or more, peroxide-decomposed polyolefin resin (a polyolefin resin that is thermally decomposed by mixing with peroxide and kneading under heat to reduce the molecular weight and increase the fluidity of the resin) ), specifically isotactic polypropylene, copolymers of propylene and 15 mol% or less of other α-olefins, such as propylene-ethylene block copolymers, propylene-1-butene copolymers, propylene-1 -Hexene copolymer, propylene-4-methyl-1-pentene copolymer with a melt index of 0.1 to 50 tr/
A time of 10 minutes is preferable from the viewpoint of flow characteristics of the thermoplastic elastomer obtained.

(b) As the polyolefin resin, the above-mentioned peroxide decomposition type polyolefin resin, peroxide crosslinked polyolefin resin (polyolefin resin crosslinked by mixing with peroxide and kneading under heating to reduce the fluidity of the resin), For example, density 0.910~
0.940 low, medium, and high density polyethylene in a weight ratio of 10010 to 30/70, especially 40/20 to 20/40.
It is preferable to use a mixture obtained by mixing the above because it has excellent moldability.

In the present invention, the polyolefin resin (b) obtained as follows is used. That is, as a catalyst, (i
ii) a highly active titanium solid catalyst component containing magnesium, titanium, and halogen as essential components, (ii) an organometallic compound catalyst component, and (iii) an electron donor catalyst component (
A polyolefin obtained by polymerizing an α-olefin using a catalyst formed from (iii) in which the child donor catalyst component may be previously contained in the highly active titanium solid catalyst component. Resin is used.

Specifically, the catalyst used in producing the polyolefin resin (b) in the present invention specifically takes one of the following three forms (a) to (c).

(a) (iii) A highly active titanium solid catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components, (ii) An organometallic compound catalyst component of metals from Groups 1 to 3 of the periodic table, (iii) ) Electron donor catalyst component.

(b) (iii) Highly active titanium solid catalyst component containing magnesium, titanium and halogen as essential components, (ii) Organometallic compound catalyst component of metals from Groups 1 to 3 of the periodic table, (iii) Electron donor Catalyst component.

(c) (iii) A highly active titanium solid catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components; (11) An organometallic compound catalyst component of metals from Groups 1 to 3 of the periodic table; The present invention So, among the above @, (a) is preferable.

In the present invention, (iii) the electron donor catalyst component is preferably (i-^) a transition metal compound catalyst component soluble in an inert medium and/or <1-8) an organosilicon compound or a highly sterically hindered amine. 1.(iii) A highly active titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, (iii) above, (i-^) and/or <1
A polyolefin resin is used which is obtained by polymerizing an α-olefin using a catalyst formed by contacting the α-olefin in the absence of an α-olefin in an inert medium.

Further, in the present invention, (a) the general formula MgRR (R1 is an alkyl group, an aryl group, an alkoxide group, or an allyloxide group, and R
2 is an alkyl group, an aryl group, an alkoxide group, or a halogen), a tetravalent titanium halide, and optionally an electron donor are halogenated in the presence of a halogenated hydrocarbon. , a highly active titanium solid catalyst component obtained by contacting this halogenated product with a tetravalent titanium compound (b) an organoaluminum compound and (c) a child donor ((iii) and (iii) have been reacted in advance). It is also preferable to use, as the polyolefin resin (b), a polyolefin obtained by polymerizing an α-olefin using a catalyst containing the following.

The highly active titanium solid catalyst component (1) used in the present invention contains magnesium, titanium, and halogen as essential components. This titanium catalyst component (iii) contains magnesium halide with smaller microcrystals than commercially available magnesium halides, and usually has a specific surface area of about 3rd/g or more, preferably about 40 to about 1000 rT? The titanium catalyst component (iii) has a halogen/titanium (atomic ratio ) is about 5 to about 200, especially about 5 to about 100, and the electron donor/titanium (
The molar ratio) is about 0.1 to about 10, especially about 0.2 to about 6, and the magnesium/titanium (atomic ratio) is about 2 to about 10.
It is preferably about 0, particularly about 4 to about 50.

It is particularly preferred that such titanium catalyst component (iii) contains an electron donor as described above.

The component (1) may also contain electron donors, metals, elements, functional groups, etc., and may also contain organic or inorganic diluents such as silicon compounds, aluminum, polyolefins, etc. Good too.

Such particularly preferred electron donor-containing titanium catalyst components (iii) are obtained, for example, by mutual contact of magnesium compound (or magnesium metal), electron donor and titanium compound, or optionally with other reactants, For example, compounds of silicon, phosphorus, aluminum, etc. can be used.

As a method for producing such a titanium catalyst component (iii), for example, JP-A-50-108385 and JP-A-50-108385,
No. 0-126590, No. 51-20297, No. 51-
No. 28189, No. 51-64586, No. 51-928
No. 85, No. 51-136625, No. 51-87489
No. 52-100596, No. 52-147688, No. 52-104593, No. 53-2580, No. 5
No. 3-40093, No. 53-43094, No. 5-11
No. 35102, No. 56-135103, No. 56-81
No. 1, No. 56-11908, No. 56-18606,
No. 58-83006, No. 58-138705, No. 5
No. 8-138706, No. 58-138707, No. 58
No. -138708-, No. 58-138709, No. 58
-138710, 58-138715, 60-
No. 23404, No. 61-21109, No. 61-378
No. 02, No. 61-37803, No. 55-152710
It can be manufactured according to the methods disclosed in various publications such as No. Several examples of methods for producing these titanium catalyst components (iii) will be briefly described below.

(1) A magnesium compound or a complex compound of a magnesium compound and an electron donor is pulverized or not pulverized in the presence or absence of an electron donor, a grinding aid, etc. The solid obtained with or without pretreatment with a reaction aid such as a compound or a halogen-containing silicon compound is reacted with a titanium compound which is in a liquid phase under the reaction conditions. However, the electron donor is used at least once.

(2) A liquid magnesium compound having no reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid titanium complex.

(3) React the material obtained in f2) with a titanium compound.

(4) The material obtained in (1) or (2) is reacted with an electron donor and a titanium compound.

(5) A magnesium compound or a complex compound of a magnesium compound and an electron donor is ground in the presence or absence of an electron donor, a grinding aid, etc., and in the presence of a titanium compound, and the electron donor and/or The resulting solid, with or without pretreatment with reaction aids such as organoaluminum compounds and halogen-containing silicon compounds, is treated with halogens or halogen compounds or aromatic hydrocarbons. However, the electron donor is used at least once.

(6) Treating the compound obtained in (1) to (4) above with a halogen, a halogen compound, or an aromatic hydrocarbon.

Among the catalysts obtained by these preparation methods, there are catalysts obtained by using liquid titanium halide during catalyst preparation, and catalysts obtained by using halogenated hydrocarbons after or during use of the titanium compound. preferred catalysts.

Electron donors used in preparing the highly active titanium catalyst component (iii) of the present invention, so-called inside donors, include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acids, etc. Examples include oxygen-containing electron donors such as amides and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, methanol, ethanol, propatool, pentanol, hexanol, octatool, 2-
Alcohols with 1 to 18 carbon atoms such as ethylhexanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol; phenol;
Cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol,
6-2 carbon atoms which may have an alkyl group such as naphthol
5. Phenols: Ketones with 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone; Ketones with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde Aldehydes: methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl 10pionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, croton Ethyl acid, dibutyl maleate, diethyl butylmalonate,
Diethyl dibutylmalonate, ethyl cyclohexanecarboxylate, diethyl 1.2-cyclohexanedicarboxylate, di2-ethylhexyl 1.2-cyclohexanedicarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate , cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, dimethyl phthalate, diethyl phthalate , diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, organic acid esters having 2 to 30 carbon atoms such as ethylene carbonate; ethyl silicate, butyl silicate, vinyl Triethoxysilane, phenyltriethoxysilane, diphenyljethoxysilane and more! ! R acid esters; acid halides having 2 to 15 carbon atoms, such as acetyl chloride, benzoyl chloride, toluic chloride, anisyl chloride, and phthalic dichloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, Ethers with 2 to 20 carbon atoms such as anisole and diphenyl ether; Acid amides such as #acid amide, benzoic acid amide, and toluic acid amide; Acid anhydrides such as benzoic anhydride and phthalic anhydride: methylamine, ethylamine, diethylamine , tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine and other amines;
Examples include nitrile acronyms such as acetonitrile, benzonitrile, and trinitrile. Two or more types of these electron donors can be used.

The electron donor desirably contained in the titanium catalyst component is an ester, and more preferably an ester having the general formula % (wherein R1 is a substituted or unsubstituted hydrocarbon group, R2, R
5, R6 is hydrogen or a substituted or unsubstituted hydrocarbon group,
R3 and R4 are hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. In addition, R3 and R4 may be connected to each other, and the substituted hydrocarbon groups of R1 to R6 include heteroatoms such as N, 0, and S.
For example, C-0-C, C00R-C00H1OH1So
Examples include those having a skeleton represented by ), which has a group such as Hl-C-N-C-1NH2.

Particularly preferred among these are diesters of dicarboxylic acids in which at least one of R1 and R2 is an alkyl group having 2 or more carbon atoms.

Preferred specific examples of the polyvalent carboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, dibutyl malonate, diethyl methyl malonate, diethyl ethyl malonate, and diethyl inglobil malonate. , diethyl butyl malonate, diethyl phenyl malonate, diethyl malonate, diethyl dibutyl malonate, diethyl allyl malonate, di-n-butyl diethyl malonate, dimethyl maleate, monooctyl maleate, dioctyl maleate, dibutyl maleate, butyl maleate dibutyl acid, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethyl succinate,
Aliphatic polycarboxylic acid esters such as di-2-ethylhexyl fumarate, diethyl itaconate, dibutyl itaconate, dioctyl citraconate, dimethyl citraconate, diethyl 1,2-cyclohexanecarboxylate, 1゜2
-Alicyclic polycarboxylic acid esters such as diisobutyl cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadizucate, monoethyl phthalate, dimethyl phthalate, methyl phthalate, thylethyl phthalate, monoisobutyl phthalate, mono-n-butyl phthalate , diethyl phthalate, ethyl inbutyl phthalate, ethyl n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-hebutyl phthalate, phthalic acid Di-2-ethylhexyl, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate, etc. Examples include aromatic polycarboxylic acid esters and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

Preferred specific examples of polyvalent hydroxy compound esters include 1,2-diacetoxybenzene, 1-methyl-2,3-diacetoxybenzene, 2,3-diacetoxynaphthalene, ethylene glycol dibiparate, butanediol pivalate. etc. can be mentioned.

Examples of esters of hydroxy-substituted carboxylic acids include benzoylethyl salicylate, acetyl isobutyl salicylate, acetyl methyl salicylate, and the like.

Other examples of polyvalent carboxylic acid esters that can be supported in the titanium catalyst component include diethyl adipate,
Diisobutyl adipate, diisopropyl sebacate,
Di-n-butyl sebacate, di-n-octyl sebacate,
Mention may be made of esters of long-chain dicarboxylic acids such as di-2-ethylhexyl sebacate.

Among these polyfunctional esters, preferred are those having the skeleton of the general formula described above, and more preferred are esters of phthalic acid, maleic acid, substituted malonic acid, etc., and alcohols having 2 or more carbon atoms. Particularly preferred is a diester of phthalic acid and an alcohol having 2 or more carbon atoms.

Other electron donor components that can be supported on the titanium catalyst component include RCOOR- (R, R- is a hydrocarbyl group which may have a substituent, at least one of which is branched (alicyclic or (containing) or a ring-containing chain group). For example, as R and/or R-, <Cl-l3), ,C
H-1C2HsCH(CH3) -, (CH3)
2 CHCH2-, CHCH(CH3) (CH3)3C-, 25 CH2-, (Koni>-CH2-, CH3<7% CH
2-, which may exist, if either R or R' is a group as described above, the other may be the group described above, or may be another group, such as a linear or cyclic group. You can.

Specifically, dimethyl #acid, trimethylacetic acid, α-methylbutyric acid, β-methylbutyric acid, methacrylic acid, benzoyl #
Examples include various monoesters of acids, and various monocarboxylic acid esters of alcohols such as inpropatol, isobutyl alcohol, and tart-butyl alcohol.

Further, when preparing the highly active titanium catalyst component (1), a carbonate ester can be used as an electron donor. Specific examples include diethyl carbonate, ethylene carbonate, diisopropyl carbonate, phenylethyl carbonate, diphenyl carbonate, and the like.

As the electron donor used in preparing these highly active titanium catalyst components (iii), organic acid esters are particularly preferred, and specifically benzoic acid esters, phthalic acid esters, and toluic acid esters are particularly preferred.

These electron donors are combined with a highly active titanium solid catalyst component (ii
When supporting i), it is not necessarily necessary to use these as starting materials, and compounds that can be converted into these during the preparation of the titanium catalyst component may be used and converted into these compounds at the preparation stage.

Although other electron donors may coexist in the titanium catalyst component, their coexistence in too large a quantity will have an adverse effect, so they should be kept to a small amount.

In the present invention, the magnesium compound used to prepare the solid titanium catalyst component (1) is a magnesium compound that may or may not have reducing ability. Examples of magnesium compounds having reducing ability include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, Examples include ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, and butylmagnesium hydride. These magnesium compounds can be used, for example, in the form of a complex compound with an organic aluminum or the like. Further, the magnesium compound as shown in "-" may be in a liquid state or a solid state.

Magnesium compounds without reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, and octoxymagnesium chloride. Alkoxymagnesium halides such as: phenoxymagnesium chloride, methylphenoxymagnesium chloride and other allyloxymagnesium halides; jetoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, di-n-
Dialkoxymagnesium such as octoxymagnesium, alkoxymagnesium such as monoalkoxymagnesium such as 2-ethylhexoxymagnesium; allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate. etc. are used. In addition, these magnesium compounds without reducing ability may be derived from the above-mentioned magnesium compounds having reducing ability, or may be derived during the preparation of the catalyst component, such as magnesium compounds having reducing ability and polysiloxane. By contacting the compound with a compound such as a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, or an alcohol, it can be converted into a magnesium compound that does not have reducing ability. In addition, the magnesium compound may be a complex compound with another total compound, a composite compound, or a mixture with other metal compounds, and may also be a mixture of two or more of these compounds. Preferred magnesium compounds are those that do not have reducing ability, and particularly preferred are halogen-containing magnesium compounds, particularly halogen-containing magnesium such as magnesium chloride, alkoxymagnesium chloride, allyloxymagnesium chloride, or dialkoxymagnesium such as jetoxymagnesium. .

In the present invention, the titanium compound used for preparing the solid titanium catalyst component (1) is usually Ti(OR>
A tetravalent titanium compound represented by X (R is a hydrocarbon group, X is halo 4-g, 0≦g≦4) is preferred. More specifically, titanium tetrahalides such as T1Cl, TiBr, Ti14: Ti(OC1-I3) CI
3, Ti(QCH) CI,'I'1(0-n-C
4H9) CI, Ti(QCH)Br,
Trihalogenated alkoxytitanium such as Ti(0-iso-C4H9)Br3; Ti(OCH) CI
, Ti(0C2Hs)2C12,T+(0-n
-C4H9) 2 C1, Ti(QC2H5)2Br2
Dihalogenated alkoxytitanium such as Ti(OCH3
) 3C1, Ti (QC2H5) 3C1+ Ti
(0-n-C4H9)3CI,"T'1(QC2H5
) Monohalogenated trialkoxytitanium such as 3Br; T l (OCH3) 4, Ti(QCH),
Examples include tetraalkoxytitanium such as Ti(0-n-C4H9)4. Of these,
Halogen-containing titanium compounds, particularly titanium tetrahalides are preferred, and titanium shikaka is particularly preferred; these titanium compounds may be used alone or in the form of mixtures, or may be combined with hydrocarbons or halogenated hydrocarbons. It may be diluted and used.

In the preparation of the titanium catalyst component (iii), a titanium compound, a magnesium compound and an electron donor such as an organic acid ester, an alcohol, a phenol, a silicon compound,
The amount of the aluminum compound etc. to be used varies depending on the preparation method and cannot be absolutely specified, but for example, the amount of electron donor is 0.05 to 5 moles per 1 mole of the magnesium compound.
Further, the titanium compound is used in an amount of 0.05 to 500 moles.

Examples of the halogen atom constituting the titanium catalyst component include fluorine, chlorine, bromine, iodine, or a mixture thereof, with chlorine being particularly preferred.

In the present invention, the above titanium solid catalyst component N
), an organometallic compound catalyst component (it ) of a metal from Group 1 to Group 3 of the periodic table, such as an organoaluminum compound catalyst component, and an electron donor catalyst component (ii) described below.
Polymerization or copolymerization of olefins is carried out using the catalyst combination of i).

As the organometallic compound catalyst component (11) of metals from Groups 1 to 3 of the Periodic Table, (a) organoaluminum compounds having at least one A1-carbon bond in the molecule, for example, general formula (where R and R2 are hydrocarbon groups containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other, X is halogen, and m is O<m
≦3, n is 0≦n<3, p is 0≦p<3, q is a number 0≦q3, and m+nfp
+q=3) Organoaluminum compound 1 represented by (b) general formula % formula % (where Ml is Li, Na, or Ni, and R1 is the same as above) Alkylated product of metal and aluminum, (c) General formula % formula % (Here, R1 and R2 are the same as above.

A dialkyl compound of a Group 2 metal represented by M2 is MQ, Zn, or Cd can be used.

Examples of the organoaluminum compounds that belong to (a) above include the following.

General formula R11A1(OR2) -n (where R1 and R2 are the same as above, 0m is preferably a number of 1.5≦m<3), general formula R
1Al 3)
, (Here, R1 and R2 are the same as above. X is a halogen, O<m≦3.0≦n<3.0≦q<3, and m + n + q = 3 ) can be exemplified.

Specifically, the aluminum compounds belonging to (a) include trialkylaluminum such as triethylaluminum and tributylaluminium, trialkenylaluminum such as triisoprenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide, Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquichloride, RAt(OR) 2,5
Partially alkoxylated aluminum alkyls having an average composition of Alkylaluminium sesquihalogenides such as aluminum sesquipromide, partially halogenated alkylaluminiums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, diethylaluminum hydride, dibutylaluminum hydride Partially hydrogenated alkylaluminum, ethylaluminum ethoxy chloride, such as dialkylaluminum dihydride, ethylaluminum dihydride, probylaluminum dihydride, etc.
Partially alkoxylated and halogenated alkylaluminiums are used, such as butylaluminum butoxychloride, ethylaluminum ethoxybromide, and the like.

Compounds belonging to l1ir (b) include LiAl(
CH), LiAl(C7H15) 4S):, and as a compound belonging to the above (C), diethyl sub 1; (
, diethylmagnesium, etc. are used. Alkylmagnesium halides such as ethylmagnesium chloride can also be used. Among these, it is particularly preferable to use trialkylaluminum, alkylaluminum halide, a mixture thereof, and the like.

As the so-called outside donor of the four-electron contact component (iii), an electron donor similar to that used in preparing the highly active titanium solid catalyst component (iii) can be used.

Further, as the electron donor catalyst component (iii) as an outside donor, (ii-^) a transition metal compound catalyst component soluble in an inert medium, (i-B) an organosilicon compound, amines with large steric hindrance, (i-C) It is preferable to use an R acid ester or a mixed component thereof.

As such a transition metal compound catalyst component (i-A), a transition metal compound that is soluble in an inert medium is used, and specifically, a compound of a metal in the Periodic Table 'JjJVB group such as titanium, zirconium, or hafnium, Inert medium-soluble compounds of metals such as vanadium and chromium, such as halides such as chloride, bromide and iodide, alkoxides such as methoxy, ethoxide and propoxide, are used. Specifically, preferred examples of these transition metal compounds include tetravalent titanium compounds usually represented by Ti(OR) be. More specifically, TiC1, TiBr
, Ti I4, and other titanium tetrahalides; T
i (OCH) C13, T + (OCH) CI 3, T 1 (0-low CH) CI 3, Ti (QCH)
Bl-, TifO-iso-c4H9') B'3 and other trihalogenated alkoxytitaniums: T1(OCH3
) 2 CI 2 , TI (QC2Hs ) 2CI
=Ti(0-n-CH) C12,Ti(OC2H
5) Dihalogenated alkoxy titanium such as 2Br2; TitOCH3)3C1, Ti(OC2H5)3C
1, Ti(0-n-c4H9)3C1, T1(OC2H
5) Monohalokenated trialkoxytitanium such as 38r; Ti(OCH), TifOCH), Ti(0
Tetraalkoxytitanium such as -n-c4H9)4 or a mixture of these and a metal compound such as an aluminum compound or a silicon compound is used. Among these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred, and titanium tetrachloride is particularly preferred.

In addition, vanadium compounds as transition metal compound catalyst components, specifically VOCl, VO14, VO(OCH
)C1,■0(OC2H5)CI,VO(QCH
) CI, VO2251,51,5 (OCH3)2C1, ■0(OC2I(5)3, etc.) are used.

The organosilicon compound as the catalyst component (1-8) used in the present invention is generally 5i-0-C or 5iN
A compound having a C bond, such as alkoxysilane, aryloxysilane
c) etc. are used. Specifically, the formula R5i(OR>
(In the formula, 0≦n≦3, Rn
4-n is a hydrocarbon group such as an alkyl group, a cycloalkyl group,
an aryl group, an alkenyl group, a haloalkyl group, an aminoalkyl group, etc., or a halogen; R1 is a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxyalkyl group, etc.;
However, a silicon compound represented by (n R1(4-n) OR1 groups may be the same or different) is used. In addition, as an organosilicon compound, OR1
Siloxanes having groups, carboxylic acid silyl esters, etc. are used. Further, as the organosilicon compound, a compound in which two or more silicon atoms are bonded to each other via an oxygen or nitrogen atom is used.

Such organosilicon compounds can be produced by reacting a compound without a 5i-0-C bond with a compound having an O-C bond in advance or by reacting them at the polymerization site.
Examples of such organosilicon compounds that may be converted into compounds having bonds include halogen-containing silane compounds or silicon hydrides that do not have 5i-0-C bonds, aluminum compounds containing alkoxy groups, and magnesium compounds containing alkoxy groups. Examples include combinations with compounds, other metal alcoholades, alcohols, formic acid esters, ethylene oxides, and the like. The organosilicon compound may also contain other metals (eg, aluminum, tin, etc.).

Specifically, such organosilicon compounds include trimethylmethoxysilane, trimethylethoxysilane,
Dimethyldimethoxysilane, dimethyljethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, Bis(0-)lyldimethoxysilane, bis-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-tolyldimethoxysilane,
Bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane,
n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane
-oxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, 1SO-butyltriethoxysilane, phenyl 1- ethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane,
Vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltrimethoxysilane Allyloxy (a I ly f
oxy) silane, vinyltolyl (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, especially ethyltriethoxysilane, n-propyltriethoxysilane,
t-Butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyl Methyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyljethoxysilane, ethyl silicate, and the like are used.

In addition, the amines with large steric hindrance include 2.2,
6,6-titramethylbiperidine, 2,2,5,5-tetramethylpyrrolidine, or derivatives thereof, tetramethylmethylenediamine, etc. are used.

The component (ii4) can also be used in the form of an adduct with other compounds.

As the electron donor catalyst component (1i) as an outside donor, organic acid esters such as benzoic acid esters, phthalic acid esters, toluic acid esters (such as methyl toluate) as described above, or 5i-
Particularly preferred are organosilicon compounds having 0-C bonds.

The catalyst used in the olefin polymerization method of the present invention is formed by contacting the above components (iii), (ii), and (i>) in an inert medium in the absence of an α-olefin. Various contacting methods can be considered depending on the order of contacting each component, and any contacting method can be adopted.

In the method of the present invention, it is preferable that the proportions of each component when contacting component (iii), component (ii), and component (iii) in an inert medium are as follows: (i)
The ratio of metal atoms M9 of component (11) to 1 gram atom of titanium of component ii) is usually 1 to 50 gram atoms,
Preferably in the range 2-30 gram atoms, (iii
The ratio of component (iii) to 1 gram atom of titanium in component () is usually 0.3 to 10 moles, preferably 0.7 to 5 moles.
The ratio of the transition metal atom M2 of component (i-A) to 1 gram atom of titanium of component (iii) is usually 0.1 to 10 gram atom, preferably in the molar range.
Preferably it is in the range of 0.4 to 3 gram atoms.

Further, the above-mentioned contact treatment is preferably carried out in an inert medium, and examples of such inert medium include ethane, propane, butane, pentane, methylpentane, hexane, heptane, octane, decane, gasoline, kerosene, Aliphatic hydrocarbons such as light oil, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene are used.
It is also possible to use a mixture of two or more of these.

Furthermore, the temperature during the above-mentioned contact treatment is usually -50 to 1
．． OO''C5 is preferably -20 to 30 degrees Celsius, and the time required for the contact treatment is usually in the range of 1 minute to 10 hours, preferably 5 minutes to 2 hours.

Such contact treatment of each catalyst component is carried out in the absence of the olefin component, so that the catalyst used in the process of the invention is formed in suspension. The catalyst can be used as a suspension as it is, or the catalyst produced from the suspension can be separated and used.

The polyolefin used in the present invention is obtained by polymerizing an olefin using the catalyst formed by the above contact treatment. The polymerization reaction of olefins can usually be carried out in the above-mentioned inert medium,
It can be carried out in an α-olefin medium as a polymerization raw material. In addition, only the catalyst formed in the above contact treatment can be used in the polymerization reaction which can be carried out in a mixed medium of these, and in addition to the catalyst formed in the above contact treatment, component (iii), It is also possible to use a catalyst obtained by contacting any one to three components of component (i-A) and component (i-8>) with the above catalyst.

In this case, the contact treatment may be performed in the absence of an olefin or in the presence of an olefin.

When obtaining the polyolefin used in the present invention, the olefin polymerization is carried out in a gas phase or in a liquid phase, such as a slurry, but a gas phase method is particularly preferred. In slurry polymerization, an inert hydrocarbon is used as a solvent as well. In the case of hexapolymerization, in which the olefin itself may be used as a heating medium, the above-mentioned (i>component, (j) component, (
Polymerization can be carried out using only the catalyst formed by the pre-contact treatment of component (iii), or in addition to the catalyst formed by the pre-contact treatment of component (1), (iii), and (iii). Furthermore, (ii > component, (
Polymerization can be carried out with the addition of component (iii) or a mixture of components (iii) and (iii).

The proportion of each catalyst component present in the polymerization reaction system is approximately o, oo in terms of T1 atoms for the catalyst component (iii).
t ~ about 0.5 milligram atom/1, especially about 0.00
5 to about 0.5 milligram atom/1, and for the catalyst component (ii), the metal atom in the component (11) is about 1 gram atom of titanium in the catalyst component (iii). 1 to about 2000 gram atoms, preferably about 5
~about 500 gram atoms, and the catalyst component <
Regarding i-8), the amount of component (ii-8) is about 0.1 to about 500 mol, preferably about 0.5 to 100 mol, per 1 gram atom of titanium in the catalyst component (iii). range.

In the polymerization reaction, when polymerization is carried out by adding the catalyst component (ii) in addition to the catalyst formed by the preliminary contact treatment, the proportion of the component (11) is the same as the catalyst component (ii).
per gram atom of titanium in (iii)
) The metal atoms in the component range from about 1 to about 2000 gram atoms, preferably from about 10 to about 500 gram atoms. Similarly, when performing polymerization by adding the catalyst component (1-8) in addition to the catalyst formed by the preliminary contact treatment, the addition ratio of the catalyst component (1-8) is
ii) about 0 to 1000 per gram atom of titanium in
moles, preferably in the range of about 0 to about 100 moles.

The olefin polymerization temperature is preferably about 20 to about 200°C,
- The layer temperature is preferably about 50 to about 120°C, and the pressure is normal pressure to about 100 kg/cj, preferably about 2 to about 120°C.
The zero polymerization, which is preferably about 50 hr/-, can be carried out in any of the batch, semi-continuous and continuous methods. Furthermore, it is also possible to carry out the polymerization in two or more stages under different reaction conditions.

Using such a catalyst, a polymer with a high stereoregularity index can be produced with high catalytic efficiency, especially when applied to the stereoregular polymerization of an α-olefin having 3 or more carbon atoms.

In order to prepare the thermoplastic elastomer composition in the present invention, for 100 parts by weight of a blend obtained by mixing (a) ethylene/α-olefin copolymer rubber and (b) polyolefin resin as described above, About 0.01 to 2% by weight, preferably 0.03 to 1.0% by weight, more preferably 0.05 to 0.5% by weight of a crosslinking agent is blended and dynamically heat treated to partially or completely Crosslinking may be performed.

In this case, (a) the ethylene/α-olefin copolymer rubber is used in an amount of 100 to 10 parts by weight, preferably 90 to 20 parts by weight, and (b) the polyolefin resin is used in an amount of 0 to 90 parts by weight, preferably 10 to 20 parts by weight. 80 parts by weight amount (a) + (
b) is preferably mixed in an amount selected to be 100 parts by weight.

Dynamic heat treatment here means kneading in a molten state. In this case, the kneading device may be an open type device such as a mixing roll or a Banbury mixer 1.
Closed equipment such as extruders, kneaders or continuous mixers may be used.

The kneading is preferably carried out in a non-release type device, preferably in an inert gas atmosphere such as nitrogen or carbon dioxide, and the temperature is usually 150 to 280°C, preferably 170 to 240°C. , kneading time is usually 1 to 20
minutes, preferably 1 to 10 minutes.

Crosslinking agents used for partial or complete crosslinking include organic peroxides, sulfur, phenolic vulcanizing agents,
Oximes, polyamines, etc. are used, and among these, organic peroxides and phenolic vulcanizing agents are preferred from the viewpoint of the physical properties of the thermoplastic elastomer obtained.

As the phenolic vulcanizing agent, an alkylphenol formaldehyde resin, a triazine-formaldehyde resin, and a melamine-formaldehyde resin can be used.

Examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and 2,5-dimethyl-2,5-bis(tert-butylperoxide).
butylperoxy)hexyne-3,1,3-bis(ta
rt-butylperoxyisopropyl)benzene, 1,
1-bis(tart-butylperoxy) -3,3,
5-trimethylcyclohexane, n-butyl-4,4-
Bispert-butylperoxy)valerate, dibenzoylperoxide, tert-butylperoxybenzoate, and the like can be used. Among these, bisperoxide compounds are preferred because they have little odor and high scorch stability, and 1,3-bis(tert-butylperoxyisopropyl)benzene is particularly optimal.

In addition, when performing partial or complete crosslinking, crosslinking aids such as p-quinone dioxime, l), D'-dibenzoylquinone dioxime, or divinylbenzene (DV
B) By blending a polyfunctionality such as diethylene glycol methacrylate or polyethylene diglycol methacrylate with a nil monomer, a more uniform and mild crosslinking reaction can be achieved. Divinylbenzene (DVB) is particularly preferred, as it has a homogeneous crosslinking effect upon heat treatment and provides a thermoplastic elastomer with well-balanced fluidity and physical properties.

The blending amount of divinylbenzene (DVB) is 100% of the composition.
0.05 to 2 parts by weight, preferably 0.1 to 2 parts by weight
It is 1.5 parts by weight.

The partially or completely crosslinked thermoplastic elastomer thus obtained has a gel content extracted in cyclohexane of 10% by weight, determined as follows:
Above, preferably 40 to 100% by weight, more preferably 80 to 99.5% by weight, particularly preferably 80 to 96% by weight
It is desirable that

Here, the measurement of the cyclohexane-extracted gel content is performed as follows. Sample pellet of thermoplastic elastomer (
Weigh out approximately 100 cm of each pellet (size: 1+w x 1++ m x 0.5M), immerse it in 30 cc of cyclohexane in a closed container at 23°C for 48 hours, then take out the sample and dry it.

If the thermoplastic elastomer contains cyclohexane-insoluble fillers, pigments, etc., the weight of the cyclohexane-insoluble fillers, pigments, etc. other than the polymer components is subtracted from the weight of this dry residue after drying. The corrected final weight (Y) is taken as the corrected final weight (Y), while cyclohexane-soluble components other than the ethylene/α-olefin copolymer are calculated from the weight of the sample pellet, such as mineral oil, plastic-a + cyclohexane-soluble rubber components, and thermoplastics. If the elastomer contains cyclohexane-insoluble fillers, pigments, etc., the corrected initial weight ( X).

From these values, the cyclohexane extracted gel content is determined by the following formula.

Corrected final weight (Y) Gel content (χ) = It is preferred that the heated xylene extracted gel contains 2 to 80% by weight, particularly 5 to 60% by weight.

The thermal xylene extracted gel content is measured as follows. That is, sample pellets (each pellet size 23
Accurately weigh approximately 0.3 g of the city (X3m, XB surface), and define this weight as the initial type jl (X).

Next, this sample pellet was immersed in 80 ml of boiling xylene in a closed container for 5 hours, filtered through a 325 mesh screen, air-dried the residue on the screen, and then vacuum-dried at 80°C for 5 hours. , the amount of this dry residue is the final weight (Y).

If the thermoplastic elastomer contains thermally xylene-insoluble fillers, pigments, etc., subtract the weight of these thermally xylene-insoluble fillers, pigments, etc. from the weight of the sample pellet and the weight of the dry residue. The weights obtained are the initial weight (X) and final weight (Y), respectively.

From these initial weight (X) and final weight (Y), the thermal xylene extracted gel content is determined by the following formula.

Final ffi amount (Y),! 8 xylene extracted gel molecules %) = -x 100 initial weight (X) The methyl ethyl ketone insolubility of the partially or completely crosslinked thermoplastic elastomer obtained as described above is measured as follows. . Approximately 100 beret samples of thermoplastic elastomer (size of each beret: 1 am x 1 nm x 0.5 mm) were weighed and added to 30 cc of methyl ethyl getone in a closed container at 23°C.
After soaking for 48 hours, the sample is taken out and dried. If the thermoplastic elastomer contains fillers, pigments, etc. that are insoluble in methyl ethyl ketone, the weight of this dry residue minus all insoluble fillers, pigments, etc. other than the polymer components is dried. On the other hand, if the thermoplastic elastomer contains fillers, pigments, etc. insoluble in methyl ethyl ketone, it is determined that the weight of the sample pellet is the corrected final weight (Y). The corrected initial form jt (X) is obtained by subtracting the weight of the components.

From these values, the methyl ethyl ketone extract is determined by the following formula.

Corrected initial weight (X) - Corrected lll amount (
Y) Extractable fraction (X)・□×100 Corrected initial weight In the thermoplastic elastomer composition according to the present invention, the above-mentioned (a) ethylene/α-olefin copolymer rubber and (b) polyolefin resin are combined. When crosslinking the mixture by dynamic heat treatment, a mixture formed by blending (C) a peroxide non-crosslinked hydrocarbon rubbery substance and/or (d) mineral oil with the above components (a) and (b). You can also use Such components (C) and/or (d
), it is possible to improve the moldability and flow characteristics of the resulting thermoplastic elastomer composition.

Examples of the peroxide non-crosslinked hydrocarbon rubber material (C) that may be blended as necessary include polyisobutylene, butyl rubber, propylene-ethylene copolymer rubber with a propylene content of 50 mol% or more, and propylene-ethylene copolymer rubber. A hydrocarbon-based rubber-like material is used that does not crosslink or reduce fluidity even when mixed with a peroxide such as 1-butene copolymer rubber or atactic polypropylene and kneaded under heating. Among these, polyisobutylene rubber,
Butyl rubber Propylene with a propyne content of 70 mol% or more
Ethylene copolymer rubber and propylene-1-butene copolymer rubber are most preferred.

(d) FFI oil usually weakens the intermolecular force of rubber when it is rolled, making it easier to process, and also helps disperse carbon black, white carbon, etc., or increases the hardness of vulcanized rubber. High-boiling point petroleum fractions are used for the purpose of reducing stiffness and increasing flexibility or elasticity. Specifically, paraffinic, naphthenic, or aromatic mineral oils are used.

Also, peroxide non-crosslinked hydrocarbon rubbery substance (C)
and/or mineral oil (d) is added to (a) ethylene-α-olefin copolymer rubber and (
b) The above (C) and/or the above (d) is 0.5 to 2 with respect to 100 parts by weight of the total IL with the polyolefin resin.
00 parts by weight, preferably 1 to 100 parts by weight, more preferably 1 to 80 parts by weight.

In addition, when the above (c) + (d) is used in a ratio of 1 to 5 parts by weight, particularly preferably 1 to 4.5 parts by weight, the moldability of the resulting thermoplastic elastomer composition and The composition has good fluidity, and the molded products obtained from the composition exhibit almost no phenomena such as blocking, bleeding, gloss staining, or fogging, and have the excellent effect of improving the flame retardancy of the molded products. is recognized.

Furthermore, in the thermoplastic elastomer composition according to the present invention,
A polyolefin resin (n) is blended into the thermoplastic elastomer composition obtained as described above, if necessary. As the polyolefin resin (II), the polyolefin resin (b) added during the dynamic heat treatment The same resins as, i.e. ethylene, propylene, butene-1
, hexene-1,4-methyl-1-pentene, etc.
Homopolymers of olefins, copolymers of two or more thereof, or copolymers of α-olefins with 15 mol% or less of other polymerizable monomers, such as ethylene-vinyl acetate copolymers, ethylene-acrylic Acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-
A resinous polymeric substance such as methyl methacrylate copolymer is used.

Melt index (ASTM-D-1238-65T) of these polyolefin resins (II).

190℃, however, in the case of propylene polymer, 23℃
0℃) is 5 to 100 tr/10 minutes, especially 10
If the polyolefin resin is added both during and after the dynamic heat treatment, which is preferably ~50 g/10 min, the polyolefin resin (b) and the polyolefin resin (]II may be of the same type or different types. good.

The thermoplastic elastomer composition according to the present invention may further contain carbon black, clay, talc, calcium carbonate, heavy calcium carbonate, kaolin, diatomaceous earth, silica, alumina, asbestos, graphite, glass fiber, etc. Fillers or antioxidants such as phenyl-α-naphthylamine, 2,6-di-tert-butylphenol, tetrakis [methylene (3,5-di-tart-butyl-4-hydroxyphenyl) propionate], i (silver agent, heat stabilizer) , flame retardants, antistatic agents, and other additive components can be blended.

These fillers or additives may be added during the preparation of the thermoplastic elastomer, or may be added after preparation when forming the thermoplastic elastomer into a molded article.

The thermoplastic elastomer composition according to the present invention can be molded using molding equipment used for ordinary thermoplastic polymers, and is suitable for extrusion molding, calendar molding, and especially injection molding.

Since the thermoplastic elastomer composition according to the present invention uses a polyolefin resin obtained by polymerizing α-olefin in the presence of a specific catalyst, it has excellent properties such as heat resistance, tensile strength, dust resistance, flexibility, and elasticity. It is possible to provide an excellent molded product that has excellent properties such that the impact resistance does not decrease even when the rigidity is increased.

Such thermoplastic elastomers are used in body panels, bumper parts, sight shields, automobile parts such as steering wheels, WfI products such as shoe soles and sandals, electrical parts such as wire sheaths, connectors, and cap plugs, golf club grips, It is used for leisure goods such as baseball bat grips, swimming fins, underwater glasses, gas getters, waterproof cloth, garden hoses, belts, etc., but is especially suitable for large thick products such as parts of bumpers. .

The present invention will be explained by examples, but the present invention is not limited to these examples in any way unless the gist of the invention is exceeded.

First, the method for producing (b) polyolefin will be explained using reference examples.

Reference Example 1 [Preparation of titanium catalyst] 1.14 h of magnesium jetoxide was placed in a 50 J reactor.
g and 15j of carbon tetrachloride were added, the temperature was raised to 75°C with stirring, and 480 alIt of ethyl benzoate and 15
Titanium tetrachloride (1) was added thereto and mixed for 2 hours at the same temperature.Then, the resulting suspension was filtered, the resulting solid portion was washed with n-hexane, and the solid portion was isolated. This solid part is 15
After resuspending the mixture in titanium tetrachloride (J) and mixing at 80° C. for 2 hours, the catalyst was washed with n-hexane to obtain a highly active Ti-containing catalyst.

[Polymerization] A polymerization reaction was carried out using one fluidized bed polymerization vessel with a reaction volume of 40 J. The titanium catalyst was continuously supplied to the fluidized bed polymerization vessel at a ratio of about 0.8 mmol Ti/Hr, and propylene and H2 gas were continuously supplied to carry out a continuous gas phase polymerization reaction. Propylene supply rate is 483ONj/Hr
The concentration ratio of hydrogen and propylene in the polymerization vessel was approximately 0.0021 molar ratio of hydrogen/propylene.

The temperature of the gas phase polymerization reaction was 80°C, and the pressure was 8 ktr/
dG, the superficial gas velocity was 40 cI+/sec, and the feed rate of the titanium catalyst was adjusted so that the amount of polymer produced was 5+r/Hr. Triethylaluminum was prepared in advance with hexane to a concentration of 200 mmol/J, and was continuously supplied to the reaction system at a rate of 51 mmol/Hr. On the other hand, methyl toluate, which had been prepared in advance with hexane to a concentration of 200 mmol/j, was added to 17 mmol/Hr.
It was supplied continuously.

Table 1 shows the basic physical properties of the obtained polymer.

A polymerization reaction was carried out by connecting two fluidized bed type polymerizers with a side-only reaction volume of 40 J in series. The catalyst prepared in Reference Example 1 was used as the catalyst, and the polymerization conditions described in Example 1 were used (however, the hydrogen/propylene ratio was 0.0021 to 0.003).
After carrying out propylene polymerization in (replaced with No. 8), the obtained polymer was continuously poured into another polymerization vessel, and copolymerization of ethylene and propylene was carried out in a polymerization vessel connected to the subsequent stage.

The polymerization reaction conditions in the latter stage are a temperature of 70°C, a pressure of 7 kr/-G, and a superficial gas velocity of 40 cm/-G.
When ethylene, hydrogen, and propylene were mixed in the polymerization reactor for 4 seconds, the ethylene □ ratio was about 0.42, and the ethylene to propylene hydrogen □ ratio was about 0.0096.

ethylene propylene Table 1 shows the basic physical properties of the obtained polymer.

! 1M unit [Preparation of titanium catalyst] 1.14k of magnesium jetoxide in a 50J reactor
Add carbon tetrachloride of r and 15j, raise the temperature to 75°C with stirring, and add 640 ml of diisobutyl phthalate and 15j.
of titanium tetrachloride was added and mixed for 2 hours at the same temperature.Then, the resulting suspension was filtered, the resulting solid portion was washed with n-hexane, and the solid portion was isolated. This solid part is 1
5j was resuspended in titanium tetrachloride, mixed at 110° C. for 2 hours, and washed with n-hexane to obtain a highly active Ti-containing tactile butterfly.

[Polymerization] Among the polymerization conditions shown in Example 1, the feed rate of the titanium catalyst was changed from about 0.8 mmol Ti/Hr to about 0.6 mmol T.
i/Hr and the ratio of hydrogen to propylene to about 0.0
021 to about 0.0016, and 17 mmol/
Example 1 except that the Hr supply of methyl toluate was replaced with 5 mmol/Hr diphenyldimethoxysilane.
Polymerization reaction of propylene was carried out in the same manner.

Table 1 shows the basic physical properties of the obtained polymer.

11 Plate A Reactor [Two 40 J fluidized bed polymerization reactors were connected in series to carry out the polymerization reaction. As a catalyst, the catalyst prepared in Example 3 was used, and the polymerization conditions described in Example 3 were used (however, the hydrogen/propylene ratio was changed from 0.0016 to 0.00).
After propylene polymerization was carried out in a polymerizer (replaced with No. 21), the obtained polymer was continuously poured into another polymerization vessel, and copolymerization of ethylene and propylene was carried out in a polymerization vessel connected to the subsequent stage.

The polymerization reaction conditions in the latter stage are a temperature of 70°C, a pressure of 71qr/aaG, and a superficial gas velocity of 40°C.
The concentrations of ethylene, hydrogen, and propylene in the polymerization reactor were C1l/sec, and the ethylene □ ratio was about 0.42, and the ethylene/propylene hydrogen □ ratio was about 0.0062.

Propylene + ethylene Table 1 shows the basic physical properties of the obtained polymer.

Hiko ■5 [Preparation of titanium catalyst] In a 50J reactor, anhydrous magnesium chloride 0°714h
g (7.5 mol), 3.8 Jl of decane, and 3.51 Jl (22° 5 mol) of 2-ethylhexyl alcohol were heated at 130°C for 2 hours to form a homogeneous solution.
170 sr (1.13 mol) of phthalic anhydride was added to this solution, and the mixture was stirred and mixed at 130° C. for an additional hour to dissolve phthalic anhydride into the homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, -20"C
The entire amount was added dropwise over 1 hour to 20 J (180 mol) of titanium tetrachloride held at . After charging, the temperature of this mixed liquid was raised to 110°C over 4 hours, and then heated to 110°C.
When the temperature reaches 0°C, diisobutyl phthalate 503a
+1 (1,875 mol) was added, and the mixture was then kept at the same temperature for 2 hours with stirring. After the completion of the 2-hour reaction, the solid portion was collected by hot filtering, and the solid portion was heated to a temperature of 27.5 J; c+
After re-Q-analyzing in Step 4, a heating reaction was carried out again at 110°C for 2 hours. 6 After completion of the reaction, the solid portion was collected again by hot filtration, and was washed with decane and hexane at 110°C. A titanium catalyst component was prepared by washing thoroughly until no free titanium compound was detected.

[Polymerization] In Example 3, the feed rate of the titanium catalyst was changed from about 0.6 mmol Ti/Hr to about 0.38 mmol Ti/Hr (alternatively, from about 0.0016 mmol Ti/Hr to about 0.0016 mmol Ti/Hr) on hydrogen and propylene. The reaction of propylene was carried out in the same manner as in Example 3, except that p was replaced with 001.5.

Table 1 shows the basic physical properties of the obtained polymer.

The polymerization reaction was carried out by connecting two fluidized bed type polymerizers having a quadratic ball reaction volume of 40 J in series. As the tentacles, the tentacles prepared in Reference Example 5 were used, and the polymerization conditions described in Example 5 (however, only the hydrogen/propylene ratio was 0.0015 to 0.00).
After propylene polymerization was carried out using the same method (replaced with No. 19), the obtained polymer was continuously poured into another polymerization vessel, and copolymerization of ethylene and propylene was carried out in the polymerization vessel connected to the subsequent stage.

The polymerization reaction conditions in the latter stage were as follows: the temperature was 70"C, the pressure was 7 ksr/cj G, and the superficial gas velocity was 40"7 seconds. The concentration of ethylene L was approximately 0.42, and the ethylene + propylene hydrogen ratio was approximately 0.0060.

Propylene + ethylene Table 1 shows the basic physical properties of the obtained polymer.

Table 1 Reference'J example MFR ethylene containing 1k rrEt71
0 min] U mol%] 1 9.8 0 96.52
21 9.4 - 3 10.3 0 97.04
20 9.6 - 5 10.6 0 - 6 19 10.7 98.5 A thermoplastic elastomer was manufactured in the following manner using the following components.

(Component A) Ethylene/propylene/ethylidenenorbornene ternary copolymer rubber: ethylene unit/propylene unit (molar ratio) near 8/22, iodine value 15, Mooney viscosity (ML, 121°C) 1+4 61, Qlii, 3. 0) (Component B) Ethylene-10-pyrene copolymer produced in Reference Example 6 (Component E) Naphthenic process oil (Component F) Divinylbenzene (Component A) 70 parts by weight, (Component B) 30 parts by weight ,(
After kneading 10 parts by weight of component E) and 0.3 parts by weight of component F in a Banbury mixer at 180°C in a nitrogen atmosphere for 5 minutes, the resulting kneaded product was cut into square pellets with a sheet cutter. .

To 100 parts by weight of this square pellet, 1,3-bis(t
ert-butylberoxyisoglobil)benzene 0.
The upper parts of the two parts were kneaded using a Henschel mixer and extruded using an extruder at 220° C. under a nitrogen atmosphere to obtain a thermoplastic elastomer having a weight of 87% xylene extracted gel.

Table 2 shows the physical properties of the thermoplastic elastomer thus obtained.

In addition, each physical property value was measured as follows.

MFR: Measured in accordance with ASTM D-1238 (230°C, 10 minutes).

Bending initial elastic modulus: Measured in accordance with ASTM D-790.

Torsional rigidity: Measured in accordance with ASTM D-1043.

Shore D hardness: Measured in accordance with ASTM D-2240.

Shore A hardness: Measured in accordance with JIS K-6301.

Permanent elongation: Measured according to JIS K-6301.

Fire 1” “L Yu””.

Example 1 was carried out in the same manner as in Example 1, except that each component as shown in Table 2 was used in the proportions shown in Table 2.

The results are shown in Table 2.

Note that the butyl rubber as (component C) has a Mooney viscosity M
L (100°C) was 45, and the degree of un1+4 saturation was 1.0 mol%. In addition, the propylene-ethylene rubber as (component D) has a propylene content of 59
mol%, ethylene content is 41 mol%, MFR (2
30° C.) was 0.4 g/10 minutes.

Claims (1)

[Claims] 1. (a) ethylene/α-olefin copolymer rubber; (b) (i) highly active titanium solid catalyst component containing magnesium, titanium, and halogen as essential components; (ii) periodic an organometallic compound catalyst component of a metal from Group 1 to Group 3 of the Table of Contents; and (iii) an electron donor catalyst component ((iii) is partially or wholly contained in (i) a highly active titanium solid catalyst component). A mixture containing as an essential component a polyolefin resin obtained by polymerizing an α-olefin using a catalyst formed from
Partially or fully crosslinked thermoplastic elastomer composition obtained by dynamic heat treatment in the presence of a crosslinking agent. 2. [I] (a) Ethylene/α-olefin copolymer rubber, (b) (i) Highly active titanium solid catalyst component containing magnesium, titanium, and halogen as essential components, (ii) No. 1 of the periodic table an organometallic compound catalyst component of Group 1 to Group 3 metals; and (iii) an electron donor catalyst component (even if (iii) is partially or wholly contained in (i) the highly active titanium solid catalyst component). A mixture containing as an essential component a polyolefin resin obtained by polymerizing an α-olefin using a catalyst formed from
Partially or completely crosslinked thermoplastic elastomer obtained by dynamic heat treatment in the presence of a crosslinking agent: 100~
5 parts by weight, and [II] polyolefin resin: 0 to 95 parts by weight.