JP2894452B2 - Alpha-olefin / aromatic vinyl random copolymer and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an α-olefin / aromatic vinyl random copolymer having excellent utility and a method for producing the same. More specifically, excellent adhesiveness, heat aging resistance and other properties, for example, adhesives, adhesives, resin modifiers,
The present invention relates to an α-olefin / aromatic vinyl random copolymer suitable for applications such as a compatibilizer and a method for producing the same.

Technical Background of the Invention Since the advent of the Ziegler-Natta catalyst composed of a transition metal compound and an organoaluminum compound, not only homopolymerization of α-olefins but also many studies have been made on copolymerization with aromatic vinyl monomers. Have been. However, these mainly relate to copolymers or copolymers of ethylene and styrene, or propylene and styrene, and are intended to improve the adhesion and coating properties of polyethylene and polypropylene. For example,
JP-165908 discloses a copolymer of propylene and styrene using a so-called Ziegler-type mixed catalyst comprising a titanium component and an organoaluminum compound component.

JP-A-59-24712 discloses a copolymer of styrene and propylene and a copolymer of styrene and ethylene produced using a catalyst in which a titanium compound is supported on magnesium halide. Are listed.

However, although these copolymers are excellent in weather resistance and heat resistance, their adhesiveness is not sufficient, and there has been a limit to use as an adhesive, for example.

The present inventors, in view of the problems associated with the prior art as described above, weather resistance, without impairing the heat resistance, as a result of intensive research on obtaining an olefin copolymer excellent in adhesion, Completed the present invention by finding that an α-olefin / aromatic vinyl random copolymer having the above-mentioned properties improved can be obtained from an α-olefin component having 4 to 5 carbon atoms and an aromatic vinyl monomer. I came to.

Object of the Invention The present invention is excellent in adhesiveness, heat aging resistance and other properties. For example, α-olefin / aromatic vinyl random copolymers suitable for applications such as pressure-sensitive adhesives, adhesives, resin modification, and compatibilizers It is intended to provide a polymer and a method for producing the polymer.

SUMMARY OF THE INVENTION The α-olefin / aromatic vinyl random copolymer according to the present invention comprises at least one α-olefin selected from the group consisting of 1-butene and 1-pentene, and an aromatic vinyl monomer. A random copolymer obtained by copolymerization, wherein (a) the structural unit derived from the α-olefin is 60 to
The structural unit derived from the aromatic vinyl monomer is in the range of 40 to 2 mol%, and (ii) the intrinsic viscosity [η] measured in decalin at 135 ° C.
(Iii) the molar composition (Ac) of the structural unit derived from the aromatic vinyl monomer in the copolymer, and the molar composition (Ac) determined by the X-ray diffraction method of the copolymer. The crystallinity (Xc) satisfies the following formula: 1 ≦ Xc ≦ 43−25 × log (Ac).

The method for producing an α-olefin / aromatic vinyl random copolymer according to the present invention comprises: (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components; and (b) an organoaluminum. In the presence of a compound catalyst component, and (c) a catalyst formed from an electron donor component, at least one α-olefin selected from the group consisting of 1-butene and 1-pentene; By copolymerizing with the body, (a) the structural unit derived from the α-olefin is 60 to
The structural unit derived from the aromatic vinyl monomer is in the range of 40 to 2 mol%, and (ii) the intrinsic viscosity [η] measured in decalin at 135 ° C.
(Iii) the molar composition (Ac) of the structural unit derived from the aromatic vinyl monomer in the copolymer, and the molar composition (Ac) determined by the X-ray diffraction method of the copolymer. It is characterized by producing an α-olefin / aromatic vinyl random copolymer having a crystallinity (Xc) satisfying the following formula: 1 ≦ Xc ≦ 43−25 × log (Ac).

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the α-olefin / aromatic vinyl random copolymer according to the present invention and a method for producing the same will be specifically described.

The α-olefin / aromatic vinyl random copolymer according to the present invention comprises a random copolymer of at least one α-olefin selected from the group consisting of 1-butene and 1-pentene, and an aromatic vinyl monomer. It is united.

As the aromatic vinyl monomer constituting the α-olefin / aromatic vinyl random copolymer, specifically, styrene, o-methylstyrene, m-methylstyrene, p-
Alkyl-substituted styrenes such as methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, propylenestyrene and butylstyrene; halogen-substituted styrenes such as chlorostyrene and bromostyrene;
Vinyl naphthalene such as vinyl naphthalene, 2-vinyl naphthalene, 1-vinyl-4-methylnaphthalene and the like are used, preferably styrene and p-methylstyrene are used, and particularly preferably styrene is used. One of these aromatic vinyl monomers may be used alone, or two or more thereof may be used in combination.

Further, in addition to the above monomers, other copolymerizable monomers such as ethylene, propylene, hexene-1, and the like are included in the α-olefin / aromatic vinyl random copolymer.
Heptene-1, octene-1, nonene-1, decene-
1, undecene-1, dodecene-1 and the like can be copolymerized within a range not to impair the object of the present invention.

In the α-olefin / aromatic vinyl random copolymer, structural units derived from the α-olefin are 60
9898 mol%, preferably 60-96 mol%, more preferably 70-96 mol%, and the structural unit derived from the aromatic vinyl monomer is 40-2 mol%, preferably 40-4 mol%. %, More preferably in the range of 30-4 mol%. The α
-The composition of the olefin / aromatic vinyl random copolymer was determined by measurement of ¹³ C-NMR spectrum.

The α-olefin / aromatic vinyl random copolymer of the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1 to 6 dl / g, preferably 0.2 to 5 dl / g, particularly preferably
It is in the range of 0.5-4dl / g. This characteristic value is a measure of the molecular weight of the copolymer.

The α-olefin / aromatic vinyl random copolymer of the present invention has a crystallinity of 1 to 40 as measured by X-ray diffraction.
%, Preferably in the range of 1 to 30%. Further, the aromatic vinyl monomer content (mol%) (Ac) in the copolymer and the crystallinity (Xc) of the copolymer satisfy the following formula, and Xc ≦ 43−25 × log (Ac) is preferable. Satisfies Xc ≦ 42−25 × log (Ac).

The degree of crystallinity was determined by melt-pressing the α-olefin / aromatic vinyl random copolymer at 180 ° C., and then quenching the resulting 1 mm-thick press sheet for 24 hours, followed by X-ray diffraction measurement. Was.

The melt viscosity at 200 ° C. of the α-olefin / aromatic vinyl random copolymer of the present invention is in the range of 1,000 to 100,000 centipoise, preferably 2,000 to 80,000 centipoise. This characteristic value is a value that serves as a measure of coatability when the α-olefin / aromatic vinyl random copolymer of the present invention is used as an adhesive.

The α-olefin / aromatic vinyl random copolymer of the present invention has a softening point (ring and ball method) of 50 to 150 ° C., preferably 70 to 150 ° C.
In the range of ~ 130 ° C. This characteristic value is a value that is a measure of the upper limit temperature when the adhesive is used with the α-olefin / aromatic vinyl random copolymer of the present invention.

The α-olefin / aromatic vinyl random copolymer of the present invention has a carbon number of 4 to 4 in the presence of an olefin polymerization catalyst.
5 is obtained by copolymerizing an α-olefin and an aromatic vinyl monomer.

The olefin polymerization catalyst used in the copolymerization includes: (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components; (b) an organoaluminum compound catalyst component; and (c) It is formed from an electron donor component.

The solid titanium catalyst component (a) is magnesium,
It contains titanium, halogen and an electron donor as essential components, and magnesium / titanium (atomic ratio) is larger than 1, preferably 3 to 50, particularly preferably 6 to 30, and halogen / titanium (atomic ratio) Is greater than 1, preferably 4 to 100, particularly preferably 6 to 40, and the electron donor / titanium (molar ratio) is preferably 0.1 to 10, particularly preferably 0.2 to 6. Its specific surface area is preferably 3m ² / g or more, more preferably from about 40~1000m ² / g, more preferably about 100~800m ² / g. Normally, the titanium compound is not desorbed by simple means such as hexane washing at room temperature. And the X-ray spectrum shows whether the magnesium compound is microcrystallized regardless of the raw material magnesium compound used for catalyst preparation,
Or, it is desirably in a very finely crystallized state as compared with a crystallized state of an ordinary commercial product of magnesium dihalide. And it may contain other elements, metals, functional groups, etc. other than the above essential components. Further, it may be diluted with an organic or inorganic diluent.

The solid titanium catalyst component (a) is prepared by using a magnesium compound, a titanium compound, and an electron donor and bringing these compounds into contact. In the case of preparing the solid titanium catalyst component (a), depending on the case, other reaction reagents, for example, compounds such as silicon and phosphorus aluminum can be used.

As a method for preparing such a solid titanium catalyst component (a), for example, JP-A-50-108385 and JP-A-50-1265
No. 90, No. 51-20297, No. 51-28189,
Nos. 51-64586, 51-92885, 51-136625, 52-87489, 52-100596, and 52.
No. 147688, No. 52-104593, No. 53-2580, No. 53-40093, No. 53-40094, No. 55-13
No. 5102, No. 55-135103, No. 55-152710, No. 56-811, No. 56-11908, No. 56-1860
No. 6, JP-A-58-83006, JP-A-58-138705,
JP-A-58-138706, JP-A-58-138707, JP-A-58-138708
JP-A-58-138709, JP-A-58-138710, and JP-A-58-138710.
Nos. 58-138715, 60-23404, 61-21109, 61-37802, and 61-37803 can be produced according to the methods disclosed in the respective publications. .
The method for producing the solid titanium catalyst component (a) will be briefly described below.

For the preparation of the solid titanium catalyst component (a), a magnesium compound can be used. Examples of the magnesium compound include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability.

Here, as the magnesium compound having a reducing ability, for example, a compound represented by the formula X _n MgR _2-n (where n is 0 ≦ n ≦ 2, and R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group or When n is 0, two R's may be the same or different and X is a halogen, and X is a halogen).

Specific examples of the organomagnesium compound having such a reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamilmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesiumchloride, Examples thereof include butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, octyl butyl magnesium, butyl magnesium hydride and the like. These magnesium compounds can be used alone or may form a complex compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid.

Specific examples of magnesium compounds having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy chloride. Alkoxy magnesium halides such as magnesium and octoxy magnesium chloride; alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxy such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy magnesium Magnesium; allyloximers such as phenoxymagnesium and dimethylphenoxymagnesium Neshiumu; magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

The magnesium compound having no reducing ability may be a compound derived from the magnesium compound having the reducing ability described above or a compound derived at the time of preparing the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having a reducing ability, for example, a magnesium compound having a reducing ability is converted into a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. It may be brought into contact with a halogen-containing compound or a compound having an OH group or an active carbon-oxygen bond.

The magnesium compound is a magnesium compound having a reducing ability and a magnesium compound having no reducing ability as well as a complex compound, a complex compound of the above magnesium compound and another metal, or a mixture of another metal compound. You may. Further, a mixture of two or more of the above compounds may be used, and the compounds may be used in a liquid state or a solid state. When the compound is a solid, it can be liquefied using alcohols, carboxylic acids, aldehydes, amines, metal acid esters and the like.

Among these, a magnesium compound having no reducing ability is preferable, and a halogen-containing magnesium compound is particularly preferable. Among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

There are various tetravalent titanium compounds used for the preparation of the solid titanium catalyst component (a), and usually Ti (OR) _g X _4-g
(R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4). More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ )) Cl _{3, Ti (OC 2 H 5} ) Br 3, Ti (O-iso-C 4 H 9) Br trihalide such as ₃ alkoxy _{titanium; Ti (OCH 3) 2 Cl} 2, Ti (OC 2 H 5) 2 _{Cl 2, Ti (On-C} 4 H 9) 2 Cl 2, Ti (OC 2 H 5) dihalogenated dialkoxy titanium, such as _{2 Br 2; Ti (OCH 3} ) 3 Cl, Ti (OC 2 H 5) 3 Monohalogenated trialkoxy titanium such as Cl, Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti ( Examples thereof include tetraalkoxy titanium such as On-C ₄ H ₉ ) ₄ , Ti (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ . Among them, particularly preferred are titanium tetrahalides and alkoxy titanium trihalides, and particularly preferred is use of alkoxy titanium trihalides. These titanium compounds may be used alone or in combination of two or more. It may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

An electron donor is used in preparing the solid titanium catalyst component (a). Examples of such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, Nitrogen-containing electron donors such as amines, nitriles and isocyanates can be used. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol,
C 1 -carbon such as dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol
Alcohols having 18 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol; acetone, methyl ethyl ketone, methyl isobutyl ketone C3-15 ketones such as, acetophenone, benzophenone, cyclohexanone, benzoquinone; C2-15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate , Ethyl acetate, vinyl acetate,
Propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, benzoate Propyl acid butyl, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethoxy benzoate Organic acid esters having 2 to 18 carbon atoms such as ethyl acid, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride and the like C2 to C15 acid halides; C2 to C20 ethers such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acetic acid N, N-dimethylamide, benzoic acid Acid amides such as N, N-diethylamide, toluic acid N, N-dimethylamide; methylamine, ethylamine, diethylamine, trimethylamine, triethylamine, tributylamine,
Amines such as piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile and trinitrile; P- such as trimethyl phosphite and triethyl phosphite
Organic phosphorus compounds having an OC bond; examples thereof include alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane.

Further, as the organic acid ester, a polycarboxylic acid ester can be mentioned as a particularly preferred example,
As such a polycarboxylic acid ester, the following general formula (However, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² ,
R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group,
R ³ and R ⁴ are hydrogen or a substituted or unsubstituted hydrocarbon group, preferably at least one of them is a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ may be linked to each other. Often, when the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent contains a heteroatom such as N, O, S, etc.
O-C, COOR, COOH, OH, SO 3 H, -C-N-C-, NH 2
And a skeleton represented by the following formula:

As such polycarboxylic acid esters, specifically, diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate , Diethyl butylmalonate, diethylphenylmalonate, diethyldiethylmalonate, diethyldibutylmalonate, monooctylmaleate, dioctylmaleate, dibutylmaleate, dibutylbutylmaleate, diethylbutylbutylmaleate, diisopropylβ-methylglutarate , Diallyl ethyl succinate, di-2-ethylhexyl fumarate,
Aliphatic polycarboxylic acid esters such as diethyl itaconate, dioctyl citraconic acid, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate Esters, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate,
Ethyl isobutyl phthalate, di-n-propyl phthalate,
Diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, Aromatic polycarboxylic esters such as diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate, and heterocyclic polycarboxylic esters such as 3,4-furandicarboxylic acid. Preferred examples can be given.

Other examples of the polycarboxylic acid ester include long adipates such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Esters of chain dicarboxylic acids and the like can be mentioned. Among these compounds, it is preferable to use a carboxylic acid ester, particularly a polyvalent carboxylic acid ester,
Particularly, phthalic esters are preferably used.

The electron donor preferably contained in the solid titanium catalyst component (a) is an ester of an organic or inorganic acid, an alkoxysilane compound, an aryloxysilane compound, an ether, a ketone, a tertiary amine, an acid halide, an acid anhydride. Compounds having no active hydrogen, such as organic acid esters, alkoxysilane compounds, and aryloxysilane compounds. Among them, esters of an aromatic monocarboxylic acid and an alcohol having 1 to 8 carbon atoms, malonic acid, Substituted malonic acid, substituted succinic acid, maleic acid, substituted maleic acid, 1,
Esters of dicarboxylic acids such as 2-cyclohexyldicarboxylic acid and phthalic acid with alcohols having 2 or more carbon atoms are particularly preferred.

These electron donors do not necessarily need to be used as starting materials, and can be produced in the process of preparing the solid titanium catalyst component. Further, the solid titanium catalyst component, the magnesium compound, the titanium compound and
If necessary, a carrier compound, a reaction aid, or the like may be used in addition to the electron donor to bring them into contact with each other.

Such carrier compounds include Al ₂ O ₃ , SiO ₂ , B
Resins such as ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, ZnO ₂ , SnO ₂ , BaO, ThO, and styrene-divinylbenzene copolymer are used. Among them, Al ₂ O ₃ , SiO ₂ and styrene
Divinylbenzene copolymer is preferred.

Organic and inorganic compounds containing silicon, phosphorus, aluminum and the like can be used as reaction aids.

The solid titanium catalyst component (a) is prepared by contacting a magnesium compound, a titanium compound, an electron donor, and, if necessary, a carrier compound.

The method for preparing such a solid titanium catalyst component (a) is not particularly limited, but the method will be briefly described below with several examples.

(1) A method in which a magnesium compound, an electron donor, and a titanium compound are contacted and reacted in an arbitrary order. In this reaction, each component may be pretreated with an electron donor and / or a reaction auxiliary such as an organoaluminum compound or a halogen-containing silicon compound. In this method, the electron donor is used at least once.

(2) a liquid magnesium compound having no reducing ability;
A method of reacting a liquid titanium compound in the presence of an electron donor to precipitate a solid magnesium-titanium composite.

(3) A method in which a titanium compound is further reacted with the reaction product obtained in (2).

(4) The reaction product obtained in (1) or (2)
A method in which an electron donor and a titanium compound are further reacted.

(5) A method in which a solid obtained by pulverizing a magnesium compound, an electron donor, and a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. In addition, this method may include a step of pulverizing only the magnesium compound, a complex compound composed of the magnesium compound and the electron donor, or the magnesium compound and the titanium compound. Further, after the pulverization, a preliminary treatment with a reaction aid may be performed, followed by a treatment with a halogen or the like. Examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound.

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

(7) A method of contacting a reaction product of a metal oxide, an organomagnesium compound, and a halogen-containing compound with an electron donor and a titanium compound.

(8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon.

(9) A method of reacting a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium, a titanium compound, an electron donor and, if necessary, a halogen-containing compound such as a halogen-containing silicon compound.

(10) A method in which a magnesium compound in a liquid state having no reducing ability is reacted with an organoaluminum compound to precipitate a solid magnesium-aluminum complex, and then an electron donor and a titanium compound are reacted.

When the solid titanium catalyst component (a) is produced by such a method, the amount of the magnesium compound, the titanium compound and the electron donor used depends on the type, contact conditions, contact order and the like. The amount of the electron donor is preferably 0.01 mol to 1 mol.
It is used in an amount of 5 mol, particularly preferably 0.1 mol to 1 mol, and the titanium compound in a liquid state is used in an amount of 0.1 mol to 1000 mol, particularly preferably 1 mol to 200 mol.

The temperature for contacting these compounds is usually -70 ° C.
To 200 ° C, preferably 10 ° C to 150 ° C.

After completion of the reaction, the solid titanium catalyst component (a) obtained by any of the above methods can be purified by sufficiently washing it with a liquid inert hydrocarbon. Inert hydrocarbons used for this purpose include n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-
Octane, isooctane, n-decane, n-dodecane,
Aliphatic hydrocarbons such as kerosene and liquid paraffin; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and cymene; chlorobenzene; Examples thereof include halogenated hydrocarbons such as dichloroethane and mixtures thereof.

The olefin polymerization catalyst used in producing the α-olefin / aromatic vinyl random copolymer according to the present invention includes the solid titanium catalyst component (a) as described above,
It comprises an organoaluminum compound catalyst component (b) and an electron donor (c).

As the organoaluminum compound catalyst component (b), for example, (1) the general formula _{^{R 1 m Al (OR 2)}} n H p X q ( wherein, R ¹ and R ² are from 1 to 15 carbon atoms, It is preferably a hydrocarbon group containing 1 to 4, which may be the same or different from each other, X represents a halogen atom,
0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0
≦ q <a number of 3, moreover organic aluminum compound represented by a is) m + n + p + q = 3; (2) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, is K, R ¹ is the same as defined above) and a complex alkylated product of a Group I metal and aluminum.

As the organoaluminum compound belonging to the above (1), the following compounds can be exemplified.

General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably 1.
A general formula R ¹ _m AlX _3-m (where R ¹ is the same as above; X is a halogen, and m is preferably 0 <m <3); R ¹ _m AlH _3-m (wherein R ¹ is the same as above. M is preferably 2 ≦ m <3
In a), the general formula _{^{R 1 m Al (OR 2)}} n X q ( wherein, R ¹ and R ² are the same .X said halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3
And the like.

As the aluminum compound belonging to (1), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminum; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide ; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride _{^{butoxide, R 1 2.5 Al (OR 2}} ) 0.5 alkylaluminum partially alkoxylated with an average composition represented by like diethyl aluminum chloride, dibutyl Dialkylaluminum halides such as aluminum chloride and diethylaluminum bromide; ethylaluminum chloride Alkyl aluminum sesquihalides such as chloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; diethyl aluminum Dialkylaluminum hydrides such as hydride and dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as ethylaluminum dihydride and alkylaluminum dihydride such as propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethyl Alcohol such as aluminum ethoxy bromide Xylated and halogenated alkyl aluminum can be mentioned.

Examples of the compound similar to (1) include an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Such compounds include, for example, Methyl aluminoxane and the like can be mentioned.

Compounds belonging to the above (2) include LiAl (C
_{2 H 5) 4, LiAl (} C 7 H 15) 4 and the like.

Among the above (1) and (2), it is particularly preferable to use a trialkylaluminum or an alkylaluminum to which two or more aluminum compounds described above are bonded.

The olefin polymerization catalyst used in the production process of the α-olefin / aromatic vinyl random copolymer according to the present invention includes the solid titanium catalyst component (a), the organoaluminum compound catalyst component (b), and an electron donor. (C). Examples of the electron donor (c) include alcohols, phenols, ketones, aldehydes, carboxylic acids,
Esters of organic or inorganic acids, ethers, acid amides,
Oxygen-containing electron donors such as acid anhydride and alkoxysilane, and nitrogen-containing electron donors such as ammonia, amine, nitrile and isocyanate can be used.

Specific examples of the electron donor (c) include, for example, the electron donor used in the preparation of the solid titanium catalyst component (a) described above.

Further, as the electron donor (c), an organosilicon compound represented by the following general formula can be used.

R _n Si (OR ′) _4-n (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, and t-butylmethyldimethoxysilane. , T-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o
-Tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltriethyl Methoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltrimethoxysilane Ethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,
t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-
Norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate,
Trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane; cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3- Dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane; dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tri Cyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxy Sisilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane are used.

Among them, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane Silane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxy Silane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and the like are preferably used. That. These organosilicon compounds can be used as a mixture of two or more kinds. Among the various compounds as described above, the electron donor (c) is preferably an organic carboxylic acid ester or an organic silicon compound, particularly preferably an organic silicon compound.

The α-olefin / aromatic vinyl random copolymer of the present invention comprises: (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, and (b) an organoaluminum compound. A catalyst component; and (c) at least one α-olefin selected from the group consisting of 1-butene and 1-pentene, and an aromatic vinyl monomer in the presence of an olefin polymerization catalyst comprising an electron donor component. And by copolymerizing The copolymerization of the α-olefin and the aromatic vinyl monomer is usually performed in a liquid phase.

As the inert hydrocarbon medium used when copolymerizing the α-olefin and the aromatic vinyl monomer, specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene Aliphatic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; Mixtures and the like can be mentioned. At the polymerization reaction temperature described below, the liquid α-
Olefin or aromatic vinyl monomers can also be used.

The amount of each catalyst component used in the polymerization system is 1 reaction volume.
The amount of the solid titanium catalyst component (a) is about 0.001 to about 1.0 mmol, preferably about 0.005
Used in an amount of from about 0.1 mmol. The organoaluminum compound catalyst component (b) is such that the metal atom in the component (b) is about 1 to about 2000 moles, preferably about 5 to 500 moles, per mole of the titanium atom in the solid titanium catalyst component (a). It is used in a molar amount. An electron donor (c)
Is usually about 0.001 to about 10 mol, preferably about 0.01 to about 2 mol, particularly preferably about 0.05 to about 1 mol, per 1 mol of metal atom in the organoaluminum compound catalyst component (b). Used in

In the present invention, the polymerization temperature of at least one α-olefin selected from the group consisting of 1-butene and 1-pentene and the aromatic vinyl monomer can be appropriately selected, and is preferably about 20 to about 200 ° C. , More preferably about 50-
About 100 ° C, pressure can be selected appropriately, from normal pressure to about 1
00kg / cm ^2, preferably about preferably carried out under increased pressure conditions of atmospheric pressure to about 50 kg / cm ^2. The polymerization can be performed by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the proportion of the catalyst component used. However, it is most effective to add hydrogen to the polymerization system.

The olefin polymerization catalyst used in the present invention is formed from the solid titanium catalyst component (a), the organoaluminum compound catalyst component (b), and the electron donor (c) as described above. In this method, at least one α-olefin selected from the group consisting of 1-butene and 1-pentene is copolymerized with an aromatic vinyl monomer using the olefin polymerization catalyst. After preliminarily polymerizing the α-olefin using the above, the α-olefin and the aromatic vinyl monomer can be copolymerized using the catalyst.

The α-olefin / aromatic vinyl random copolymer of the present invention can be used as an adhesive for other resins and metals. Specific examples of the resin and metal include high-density, medium-density, low-density polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, ethylene-vinyl acetate copolymer, Surlyn A, and ethylene-vinyl alcohol copolymer. Coalesce, polystyrene, polyolefin resins such as these maleic anhydride grafts, polyethylene terephthalate, polyester resins such as polybutylene terephthalate, nylon-6, polyamide resins such as nylon-6,6, polycarbonate resins, iron, aluminum, Examples include zinc and tin.

Further, the α-olefin / aromatic vinyl random copolymer of the present invention can be used as a resin modifier for polypropylene, polyethylene, polystyrene and the like.

Effects of the Invention According to the present invention, adhesiveness, heat aging resistance and other properties are excellent, and for example, α-olefins / aromatics suitable for applications such as pressure-sensitive adhesives, adhesives, resin modifiers, and compatibilizers A vinyl random copolymer is obtained.

EXAMPLES Hereinafter, the present invention will be described with reference to examples.
It is not limited to these examples.

Example 1 (Preparation of solid titanium catalyst component (a)) 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 2-
After heating and reacting 390.6 g of ethylhexyl alcohol at 130 ° C. for 2 hours to form a homogeneous solution, 21.3 g of phthalic anhydride was added to the solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to obtain phthalic anhydride. Dissolved in the homogeneous solution. After cooling the thus obtained homogeneous solution to room temperature, 75 ml of the whole was dropped into 200 ml of titanium tetrachloride kept at -20 ° C over 1 hour. After completion of the charging, the temperature of the mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 5.22 g of diisobutyl phthalate was added, and the mixture was kept at the same temperature with stirring for 2 hours. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After the completion of the reaction, the solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the washing solution.
The solid titanium catalyst component (a) prepared by the above operation was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the titanium catalyst component (a) thus obtained was 2.5% by weight of titanium, 63.2% by weight of chlorine, 20.7% by weight of magnesium and 12.5% by weight of diisobutyl phthalate.

[Polymerization] 800 ml of toluene and 200 ml of styrene were charged into a 2 liter polymerization vessel equipped with a stirring blade, and nitrogen bubbling was performed for 15 minutes.
0 mmol of triisobutylaluminum and 1 mmol of trimethylmethoxysilane were charged. Thereafter, nitrogen bubbling was stopped, and butene-1 and hydrogen were continuously introduced at a rate of 150 L and 150 L per hour, respectively. This solution
The temperature was raised to 60 ° C., and 0.2 mmol of a titanium catalyst component calculated as titanium atoms was added to initiate polymerization. Polymerization is 30 at 60 ° C
Minutes. Polymerization proceeded in solution. The polymerization was stopped by adding isobutyl alcohol, the entire amount of the polymer was precipitated in a large amount of methanol, and dried in a vacuum at 120 ° C for 24 hours.
6 g of the polymer was obtained.

The butene-1 content of the polymer was 90.2 mol%, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 0.45 dl / g, and the crystallinity (Xc) measured by X-ray diffraction was 13.6%. Was.

Examples 2 to 4 The same procedures as in Example 1 were carried out except that the polymerization conditions were changed to those shown in Table 1. Table 1 shows the results.

Example 5 The butene-1 / styrene copolymer synthesized in Example 1 was uniformly melt-coated on a polyethylene terephthalate surface and allowed to cool naturally. The coating thickness was 56 μm. A biaxially stretched polypropylene film is placed on top of it, and the temperature is 120 ℃, 3kg / c
Heat sealing was performed under the conditions of m ² and 10 seconds to obtain a sample for evaluating adhesive strength. The evaluation of the adhesive strength of the sample was performed by the following method. The results are shown in Table 2.

[T-type peeling test] Measurement temperature: 0 ° C, 20 ° C, 50 ° C Peeling rate: 30cm / min [Shear Adhesive Failure Temperature (SAFT) measurement] Heating rate: 25 ° C / hour Load: 500g Example 6 Example Evaluation was performed in the same manner as in Example 5 using the butene-1 / styrene copolymer synthesized in Step 2.

 Table 2 shows the results.

──────────────────────────────────────────────────の Continuing on the front page (51) Int.Cl. ⁶ Identification symbol FI (C08F 210/14 212: 06) (72) Inventor Tetsunori Shinozaki 61-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Within Petrochemical Industry Co., Ltd. (72) Inventor Junichi Yoshitake No. 580 No. 32, Nagaura-jiku, Sodegaura-cho, Kimitsu-gun, Chiba Pref. Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-62-241909 (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 10/04-10/14 C08F 210/04-210/14 C08F 12/00-12/36 C08F 212/00-212/36 C08F 4 / 60-4/70

Claims (8)

(57) [Claims] 1. A random copolymer obtained by copolymerizing an aromatic vinyl monomer with at least one α-olefin selected from the group consisting of 1-butene and 1-pentene, A) The structural unit derived from the α-olefin is 60 to
The structural unit derived from the aromatic vinyl monomer is in the range of 40 to 2 mol%, and (ii) the intrinsic viscosity [η] measured in decalin at 135 ° C.
(Iii) the molar composition (Ac) of the structural unit derived from the aromatic vinyl monomer in the copolymer, and the molar composition (Ac) determined by the X-ray diffraction method of the copolymer. Characterized in that the crystallinity (Xc) satisfies the following formula: 1 ≦ Xc ≦ 43−25 × log (Ac). 2. An aromatic vinyl monomer comprising styrene and p
At least one selected from the group consisting of -methylstyrene
The α-olefin / aromatic vinyl random copolymer according to claim 1, wherein the α-olefin / aromatic vinyl random copolymer is a kind of aromatic vinyl monomer. 3. The α-olefin according to claim 2, wherein the aromatic vinyl monomer is styrene.
Aromatic vinyl random copolymer. 4. A catalyst formed from (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, (b) an organoaluminum compound catalyst component, and (c) an electron donor component. (A) the above α-olefin by copolymerizing at least one α-olefin selected from the group consisting of 1-butene and 1-pentene with an aromatic vinyl monomer in the presence of a catalyst Structural units derived from
The structural unit derived from the aromatic vinyl monomer is in the range of 40 to 2 mol%, and (ii) the intrinsic viscosity [η] measured in decalin at 135 ° C.
(Iii) the molar composition (Ac) of the structural unit derived from the aromatic vinyl monomer in the copolymer, and the molar composition (Ac) determined by the X-ray diffraction method of the copolymer. Is characterized by producing an α-olefin / aromatic vinyl random copolymer having a crystallinity (Xc) satisfying the following formula: 1 ≦ Xc ≦ 43−25 × log (Ac) A method for producing an aromatic vinyl random copolymer. 5. An aromatic vinyl monomer comprising styrene and p
At least one selected from the group consisting of -methylstyrene
The method for producing an α-olefin / aromatic vinyl random copolymer according to claim 4, wherein the aromatic vinyl monomer is a kind of aromatic vinyl monomer. 6. The α-olefin of claim 5, wherein the aromatic vinyl monomer is styrene.
A method for producing an aromatic vinyl random copolymer. 7. The α-olefin / aromatic vinyl random copolymer according to claim 4, wherein the electron donor contained in the solid titanium catalyst component (a) is an organic carboxylic acid ester. Manufacturing method of coalescence. 8. The α-olefin / aromatic vinyl random according to claim 4, wherein the electron donor contained in the solid titanium catalyst component (a) is a polyvalent organic carboxylic acid ester. A method for producing a copolymer.