JPH0723413B2 - 4-Methyl-1-pentene random copolymer and process for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a 4-methyl-1-pentene random copolymer and a method for producing the same.

More specifically, it relates to a 4-methyl-1-pentene random copolymer comprising a styrene component unit (A) and a 4-methyl-1-pentene component unit (B) and a method for producing the same.

[Conventional technology]

JP-A-55-165908 discloses propylene and 4-methyl-1-pentene, propylene and 3-methyl-1-butene produced by using a so-called Ziegler type mixed catalyst composed of a titanium component and an organoaluminum compound component. , Propylene and styrene, propylene and p-methylstyrene and propylene and 3,5,5-trimethyl-1-hexene copolymers are described.

Further, JP-A-59-24712 discloses a copolymer of styrene and propylene prepared by using a coordination catalyst having stereospecificity in the polymerization of propylene in which a titanium compound is supported on magnesium halide, and Copolymers of styrene and ethylene are described.

However, neither the propylene copolymer nor the ethylene copolymer described above have sufficient heat resistance, and neither sufficient rigidity nor hardness.

[Problems to be Solved by the Invention]

The present inventors have recognized the drawbacks of the conventional polyolefin copolymers described above that the heat resistance and rigidity and hardness are not sufficient, and to obtain an olefin-based random copolymer having these properties improved. As a result of earnest research,
Styrene-based monomer (A) and 4-methyl-1
The present invention has been accomplished by finding that a 4-methyl-1-pentene random copolymer having the above properties improved can be obtained from the monomer (B) containing -pentene as a main component.

Therefore, it is an object of the present invention to provide a polyolefin composition having improved heat resistance, rigidity and hardness.

Another object of the present invention is to provide a method for producing a 4-methyl-1-pentene random copolymer having improved heat resistance, rigidity and hardness.

[Means for solving problems]

According to the present invention, the above object is a 4-methyl-1-pentene random copolymer comprising a styrene component unit (A) and a 4-methyl-1-pentene component unit (B), wherein (i) a styrene component The unit (A) is in the range of 10 to 90 mol% and the 4-methyl-1-pentene component unit (B) is in the range of 10 to 90 mol%, and (ii) the intrinsic viscosity measured in decalin at 135 ° C. is 0.5. In the range of 20 to 20 dl / g, (iii) the molecular weight distribution (w / n) measured by gel permeation chromatography is 10 or less, (iv) the content of the styrene component unit in the copolymer. (a ₀₎ the ratio of the content (a ₁₎ of the copolymer of styrene component unit boiling n- heptane-in matter of for (a ₁ / a ₀₎ 0.8
The above is achieved by a 4-methyl-1-pentene random copolymer characterized by the above.

Further, according to the present invention, the above-mentioned object is (a) a magnesium compound, a general formula Ti (OR) gX _4- g
(R is a hydrocarbon group, X is a halogen, and a tetravalent titanium compound represented by 0 ≦ g ≦ 4), a diester and optionally a halogen compound (necessarily necessary when the magnesium compound or the titanium compound contains a halogen atom). Not)
A highly active titanium catalyst component containing magnesium, titanium, halogen and a diester as essential components formed by reacting each other with each other, (b) an organoaluminum compound catalyst component, and (c) an organic compound having a Si—O—C bond. By copolymerizing styrene and 4-methyl-1-pentene in the presence of a catalyst formed from a silicon compound catalyst component, 10 to 90 mol% of the styrene component unit (A) and the 4-methyl-1 -The pentene component unit (B) is in the range of 10 to 90 mol% and has an intrinsic viscosity of 0.5 measured in decalin at 135 ° C.
The molecular weight distribution (w / n) measured by gel permeation chromatography is 10 to 10 dl / g.
Or less, the co ratio of content of the styrene component unit in the polymer (a ₀₎ copolymer content of the styrene component unit boiling n- heptane-in matter of for (a ₁₎ (a ₁ / a ₀ ) is 0.8
It is achieved by the above-described method for producing a 4-methyl-1-pentene random copolymer.

The 4-methyl-1-pentene random copolymer of the present invention has greater heat resistance, rigidity, and hardness than the olefin random copolymer obtained by the prior art.

Also, in the present invention, the 4-methyl-1-pentene random copolymer shows good properties as a modifier for resins such as polystyrene and polypropylene.

Furthermore, the 4-methyl-1-pentene random copolymer of the present invention has excellent properties as a compatibilizer for a resin mixture, for example, a mixture of an olefin polymer and an aromatic vinyl polymer.

The present invention will be described in detail below.

The 4-methyl-1-pentene random copolymer of the present invention has the following formula in which it is randomly arranged. A repeating unit represented by It is a copolymer consisting essentially of repeating units represented by.

In the 4-methyl-1-pentene random copolymer of the present invention, the styrene component unit (A) is in the range of 10 to 90 mol%, preferably 10 to 80 mol%, more preferably 20 to 80 mol%. The 4-methyl-1-pente component unit (B) is 10 to 90 mol%, preferably 20 to 90 mol%.
It is in the range of 90 mol%, more preferably 20 to 80 mol%.

When the styrene component unit (A) in the 4-methyl-1-pentene random copolymer is more than 90 mol%,
It becomes a copolymer having low impact resistance, and when it is less than 10 mol%, it becomes a copolymer having low rigidity. The 4-methyl-1
When the 4-methyl-1-pentene component unit (B) in the -pentene random copolymer is more than 90 mol%,
A copolymer having low rigidity can be obtained, and if it is less than 10 mol%, the copolymer has poor impact resistance.

The 4-methyl 1-pentene random copolymer of the present invention is
The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 20 dl / g, preferably 0.5 to 10 dl / g, and more preferably 1 to 5 dl / g. The intrinsic viscosity [η] is 20d
If it is larger than l / g, the compatibility is poor and the modifying effect is not exhibited.
If it is less than 0.5 dl / g, the effect of improving impact resistance is not sufficient.

The 4-methyl-1-pentene random copolymer of the present invention has a molecular weight distribution (w / n) measured by gel permeation chromatography of 10 or less, preferably 8 or less,
It is more preferably 7 or less. The above molecular weight distribution (w /
When n) is larger than 10, the amount of low molecular weight copolymer is large and the surface non-tackiness is poor.

The value of the molecular weight distribution (w / n) was measured by Takeuchi,
The procedure was as follows according to "El Permeation Chromatography" published by Maruzen.

(1) Using a standard polystyrene of known molecular weight (Toyo Soda (manufactured by Toyo Soda Co., Ltd.) monodisperse polystyrene), the molecular weight M and its GPC (Gel Permeation Chromatograph) count are measured, and the correlation diagram between the molecular weight M and EV (Elution Volume) is calibrated. A curve was created. At this time, the concentration was 0.02 wt%.

(2) A GPC chromatograph of the sample was taken by GPC measurement, and the polystyrene-equivalent number average molecular weight n and weight average molecular weight w were calculated according to the above (1) to obtain the w / n value. The sample preparation conditions and GPC measurement conditions in that case are as follows.

[Sample preparation]

(A) The sample was dispensed into an Erlenmeyer flask together with the o-dichlorhensen solvent so that the concentration of the sample would be 0.1 wt%.

(B) Anti-aging agent 2, in the Erlenmeyer flask containing the sample,
6-di-tert-butyl-p-cresol was added at 0.05 wt% with respect to the polymer solution.

(C) The Erlenmeyer flask was heated to 140 ° C. and stirred for about 30 minutes to dissolve it.

(D) The solution was applied to GPC.

[GPC measurement conditions]

 It carried out on the following conditions.

(A) Equipment Watert (150C-ALC / GPC) (b) Column Toyo Soda (GMH type) (c) Sample volume 400 μl (d) Temperature 140 ° C. (e) Flow rate 1 ml / min 4-methyl of the present invention -1 Styrene component unit (a ₁ ) in the boiling n-heptane-soluble component of the styrene component unit content (a ₀ ) of the random copolymer
The ratio (a ₁ / a ₀ ) is 0.8 or more, preferably 0.9 or more, more preferably 1.0 or more. The ratio (a ₁ / a ₀ ) is 0.8
If it is smaller, the balance between impact strength and rigidity is poor.

The 4-methyl-1-pentene random copolymer of the present invention having the above-described characteristics is (a) a magnesium compound, a general formula Ti (OR) gX _4- g
(R is a hydrocarbon group, X is a halogen, and a tetravalent titanium compound represented by 0 ≦ g ≦ 4), a diester and optionally a halogen compound (necessarily necessary when the magnesium compound or the titanium compound contains a halogen atom). Not)
A highly active titanium catalyst component containing magnesium, titanium, halogen and a diester as essential components formed by reacting each other with each other, (b) an organoaluminum compound catalyst component, and (c) an organic compound having a Si—O—C bond. It can be produced by copolymerizing styrene and 4-methyl-1-pentene in the presence of a catalyst formed from a silicon compound catalyst component.

The highly active titanium catalyst component (a) contains magnesium, titanium, halogen and diester as essential components. As such a titanium catalyst component (a), magnesium / titanium (atomic ratio) is preferably about 2 to about 10.
0, more preferably about 4 to about 70, halogen / titanium (atomic ratio) preferably about 4 to about 100, more preferably about 6 to about 40, diester / titanium (molar ratio) preferably about 0.2 to about. Those in the range of 10, more preferably about 0.4 to about 6, are used. Further, its specific surface area is preferably about 3 m ² / g or more, more preferably about 40 m
² / g or more, more preferably about 100 m ² / g to about 800 m ² / g
Is.

Such titanium catalyst component (a) generally does not substantially eliminate the titanium compound by a simple means such as washing with hexane at room temperature. The X-ray spectrum shows amorphousness with respect to the magnesium compound regardless of the starting magnesium compound used for the catalyst preparation, or it is preferably highly amorphous compared with that of a usual commercial product of magnesium dihalide. It is in a broken state.

The titanium catalyst component (a) may contain, in addition to the above-mentioned essential components, other elements, metals, functional groups, electron donors, etc., as long as the catalyst performance is not significantly deteriorated. Further, it may be diluted with an organic or inorganic diluent. When it contains other elements, metals, diluents, etc., it may affect the specific surface area and amorphousness. In that case, when such other components are removed, the ratio as described above is removed. It is preferable that it exhibits a surface area value and is amorphous.

In order to produce the titanium catalyst component (a), a magnesium compound (or magnesium metal), a titanium compound and a diester or a diester-forming compound (compound forming a diester) are used with or without other reaction reagents. It is advisable to employ a method of contacting with. The preparation can be carried out in the same manner as a conventionally known method for preparing a highly active titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components. For example, Japanese Patent Laid-Open No. Sho 50
-108385, 50-126590, 51-20297, 51-2
8189, 51-64586, 51-92885, 51-136625
No. 52-87489, No. 53-100596, No. 52-147688
No. 52-104593, No. 53-2580, No. 53-40093,
53-43094, 55-135102, 55-135103, 5
It can be produced according to the methods disclosed in 6-811, 56-11908, 56-18606 and the like.

Several examples of the method for producing the titanium catalyst component (a) will be illustrated below.

(1) An electron donor and / or an organoaluminum, which is crushed or not crushed with or without a magnesium compound or a complex compound of a magnesium compound and an electron donor in the presence or absence of an electron donor, a crushing aid, and the like. A solid obtained by pretreatment with a reaction aid such as a compound or a halogen-containing silicon compound or without pretreatment is reacted with a titanium compound forming a liquid phase under the reaction conditions. However, the electron donor is used at least once.

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

(3) The compound obtained in (2) is further reacted with a titanium compound.

(4) An electron donor and a titanium compound are further reacted with those obtained in (1) and (2).

(5) A magnesium compound or a complex compound of a magnesium compound and an electron donor is pulverized in the presence or absence of an electron donor, a pulverization aid, etc., and in the presence of a titanium compound to obtain an electron donor and / or The solid obtained with or without a pretreatment with a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound is treated with halogen or a halogen compound or an aromatic hydrocarbon. However, the electron donor is used at least once.

Among these preparation methods, it is preferable to use a liquid titanium halide as the catalyst preparation agent, or use a halogenated hydrocarbon after or at the time of using the titanium compound.

The electron donor used in the above preparation need not be a diester or diester-forming compound only,
For example, electron donors other than diesters such as alcohols, phenols, aldehydes, ketones, ethers, carboxylic acids, carboxylic acid anhydrides, carbonic acid esters, monoesters and amines can also be used.

The diester which is an essential component in the highly active titanium catalyst component (a) is an ester of dicarboxylic acid having two carboxyl groups bonded to one carbon atom or carboxyl groups at two adjacent carbon atoms. Esters of dicarboxylic acids having attached groups are preferred. Examples of the dicarboxylic acid in the ester of such dicarboxylic acid include malonic acid, substituted malonic acid, succinic acid, substituted succinic acid, maleic acid, substituted maleic acid, fumaric acid, substituted fumaric acid, and one that forms an alicyclic ring. Alicyclic dicarboxylic acid having two carboxyl groups bonded to the carbon atoms of the above, alicyclic dicarboxylic acid having a carboxyl group bonded to two adjacent carbon atoms forming an alicyclic ring, and an aromatic having a carboxyl group at the ortho position Examples thereof include group dicarboxylic acids and dicarboxylic acid esters such as heterocyclic dicarboxylic acids having a carboxyl group at two adjacent carbon atoms forming a heterocycle.

More specific examples of the dicarboxylic acid include malonic acid; substituted malonic acids such as methylmalonic acid, ethylmalonic acid, isopropylmalonic acid, allyl malonic acid, and phenylmalonic acid; succinic acid; methylsuccinic acid.
Substituted succinic acid such as dimethylsuccinic acid, ethylsuccinic acid, methylethylsuccinic acid and itaconic acid; maleic acid; substituted maleic acid such as citraconic acid and dimethylmaleic acid, cyclopentane-1,1-dicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,6-dicarboxylic acid, cyclohexene-3,4-dicarboxylic acid, cyclohexene-4,5
-Dicarboxylic acid, nadic acid, methyl nadic acid, 1-
Aliphatic dicarboxylic acids such as allylcyclohexane-3,4-dicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid; furan-3,4-dicarboxylic acid Acid, 4,5-dihydrofuran-2,3-dicarboxylic acid, benzopyran-3,4-
A heterocyclic dicarboxylic acid such as dicarboxylic acid, pyrrole-2,3-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, indole-2,3-dicarboxylic acid; It can be illustrated.

At least one of the alcohol components of the dicarboxylic acid ester preferably has 2 or more carbon atoms, particularly preferably 3 or more carbon atoms, and particularly preferably has 2 or more carbon atoms, particularly 3 or more carbon atoms together with both alcohol components.
For example, diethyl ester of dicarboxylic acid, diisopropyl ester, di-n-propyl ester, di-n-butyl ester, diisobutyl ester, di-tert-butyl ester, diisoamyl ester, di-n-hexyl ester, di-2-ethylhexyl ester, Examples thereof include di-n-octyl ester, diisodecyl ester and ethyl n-butyl ester.

The magnesium compound used for preparing the highly active titanium catalyst component (a) is a magnesium compound with or without reducing ability. Examples of the former are magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl chloride. Magnesium, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium hydride, etc. are mentioned. These magnesium compounds can also be used in the form of complex compounds with, for example, organoaluminum,
It may be in a liquid state or a solid state. Examples of the latter magnesium compound having no reducing ability include magnesium chloride, magnesium bromide, magnesium iodide,
Magnesium halides such as magnesium fluoride; methoxymagnesium chloride. Ethoxy magnesium chloride.
Alkoxy magnesium halides such as isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride; allyloxy magnesium halides such as phenoxy magnesium chloride and methyl phenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n
-Octoxy magnesium, alkoxy magnesium such as 2-ertihexoxy magnesium; allyloxy magnesium such as phenoxy magnesium, dimethyl phenoxy magnesium: magnesium laurate,
Examples thereof include carboxylates of magnesium such as magnesium stearate. Further, these magnesium compounds having no reducing ability may be those derived from the above-mentioned magnesium compounds having reducing ability or those derived at the time of preparing the catalyst component. Further, the magnesium compound may be a complex compound with another metal, a double compound, or a mixture with another metal compound. Further, it may be a mixture of two or more of these compounds. Among these, preferred magnesium compounds are compounds having no reducing ability, particularly preferably halogen-containing magnesium compounds, especially magnesium chloride,
Alkoxy magnesium chloride and allyloxy magnesium chloride.

As the titanium compound used for preparing the titanium catalyst component (a), for example, a tetravalent titanium compound represented by Ti (OR) gX _4- g (R is a hydrocarbon group, X is a halogen, and 0≤g≤4) is preferable. Is. More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , TiI ₄ , etc .; 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 (Ois
trihalogenated alkoxytitanium such as o-C ₄ H ₉ ) Br ₃ : T
_{i (OCH 3) 2 Cl 2} , Ti (OC 2 H 5) 2 Cl 2, Ti (On-C 4 H 9) 2 C
_{l 2, Ti (OC 2 H} 5) dihalogenated alkoxy titanium such as _{2 Br 2; Ti (OCH 3} ) 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti (On-C 4 H 9)
Mono-halogenated trialkoxy titanium such as ₃ Cl and Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ), Ti (On-C
Examples thereof include tetraalkoxy titanium such as ₄ H ₉ ) ₄ . Of these, preferred are halogen-containing titanium compounds, particularly titanium tetrahalide, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in the form of a mixture. Alternatively, it may be diluted with a hydrocarbon, a halogen hydrocarbon or the like.

In the preparation of the titanium catalyst component (a), a titanium compound,
A magnesium compound and an electron donor to be supported, and optionally other electron donors,
For example, the amount of alcohol, phenol, monocarboxylic acid ester, silicon compound, aluminum compound, etc. used varies depending on the preparation method and cannot be specified unconditionally.
For example, the amount of the electron donor to be supported may be about 0.1 to about 10 mol and the titanium compound may be about 0.05 to about 1000 mol per mol of the magnesium compound.

Highly active titanium catalyst component (a) obtained as described above
And an organoaluminum compound catalyst component (b) and Si-
A combination catalyst of the organosilicon compound catalyst component (c) having an OC bond is used.

As the component (b) above. (I) at least 1 in the molecule
Organoaluminum compounds having a number of Al-carbon bonds, such as the general formula R ¹ mAl (OR ² ) nHpXq (where R ¹ and R ² are carbon atoms, usually 1 to 15, preferably 1 to 4 carbon atoms). The hydrogen groups may be the same or different, X is halogen, and m is 0 <m ≦.
3, 0 ≦ n <3, p is a number 0 ≦ p ≦ 3, q is a number 0 ≦ p <3, and m + n + p + q = 3), (ii) the general formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na, a K, R ¹ is as defined above), and the like alkyl complex compounds of group 1 metal and aluminum represented by.

Examples of the organoaluminum compound belonging to (i) above include the following. General formula R ¹ mAl (OR ² ) _3- m (wherein R ¹ is the same as above. X is halogen, m is preferably 0 <m <3), general formula R ¹ mAlH _3- m (here R ¹ is the same as above, m is preferably 2 ≦ m <3), and the general formula R ¹ mAl (OR ² ) nXq (wherein R ¹ and R ² are the same as above, X is halogen, 0 <
m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

The following compounds can be illustrated as an example of the aluminum compound which belongs to (i). Triethylaluminum,
Trialkylaluminums such as tributylaluminum: Trialkenylaluminums such as triisoprenylaluminum; Diethylaluminum ethoxide,
Dialkyl aluminum alkoxides such as dibutyl aluminum butoxide; alkyl aluminum sesqui alkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide;
¹ _2.5 ▼ Partially alkoxylated alkylaluminum having an average composition represented by Al (OR ² ) _0.5, etc .; Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; ethylaluminum sesquichloride, butyl Alkyl aluminum sesquihalides such as aluminum sesquichloride, ethyl aluminum sesquipromide; Partially halogenated alkyl aluminums such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dipromide; Diethyl aluminum hydride; Dialkyl aluminum hydrides such as dibutyl aluminum hydride; ethyl aluminum dihydride , Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as propylaluminium dihydride; partially alkoxylated and halogenated such as ethylaluminum ethoxy chloride, butylaluminum butoxide, ethylaluminum ethoxy bromide Alkyl aluminum.

Examples of the compound belonging to (ii) above include LiAl (C ₂ H ₅ ) ₄ ,
LiAl (C ₇ H _{15) 4} etc. can be exemplified.

Further, a compound similar to (i) may be an organoaluminum compound in which two or more aluminums are bound via an oxygen atom or a nitrogen atom. As such a compound,
For example _{(C 2 H 5) 2 AlOAl} (C 2 H 5) 2, (C 4 H 9) 2 AlOAl (C 4
H ₉ ) ₂ , Can be exemplified.

Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum in which two or more of the above-mentioned aluminums are bonded.

The organosilicon compound catalyst component (c) having a Si—O—C bond is, for example, alkoxysilane, aryloxysilane, or the like. Examples of such compounds include the formula RnSi (OR ¹ ) _4- n [wherein 0 ≦ n ≦ 3, R
Is a hydrocarbon group such as an alkyl group, a cycloalkyl group,
An aryl group, an alkenyl group, a haloalkyl group, an aminoalkyl group or the like; or halogen; R ¹ is a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an alkoxyalkyl group; provided that n R,
(4-n) OR ¹ groups may be the same or different]
A silicon compound represented by Other examples include siloxanes having an OR ¹ group, silyl esters of carboxylic acids, and the like.
Still another example is a compound in which two or more silicon atoms are bonded to each other via an oxygen or nitrogen atom. The above-mentioned organosilicon compound is converted into a compound having a Si-O-C bond by previously reacting a compound having no Si-O-C bond with a compound having an O-C bond, or by reacting at a polymerization site. You may use it. As such an example, for example, Si-O-C
Examples thereof include a combination of a halogen-containing silane compound or silicon hydride having no bond with an alkoxy group-containing aluminum compound, an alkoxy group-containing magnesium compound, and other metal alcoholals, alcohols, formate esters, ethylene oxide and the like. The organosilicon compound may also contain other metals (eg, aluminum, tin, etc.).

More specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, Vinyltrimethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltrisilane Ethoxysilane, chlorotriethoxysilane,
Ethyltriisopropoxysilane, vinyltributoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, diethyltetra Examples thereof include ethoxysiloxane and phenyldiethoxydiethylaminosilane.

The ratio of the amount of styrene and the amount of 4-methyl-1-pentene to be copolymerized in the method for producing a 4-methyl-1-pentene random copolymer of the present invention is 10 to 90 by weight, preferably 20 to 80, It is more preferably 30 to 70.

Monomer (A) mainly composed of vinyl aromatic compound and 4-
The copolymerization of the monomer (B) containing methyl-1-pentene as a main component can be carried out in any of the liquid phase and the gas phase, but especially under the condition that the polymer is dissolved or dispersed in the liquid phase. It is preferable to carry out. When carrying out the copolymerization in the liquid phase, an aromatic solvent and an aliphatic hydrocarbon, for example, an inert solvent such as benzene, toluene, hexane, heptane, and kerosene may be used as a reaction medium, but styrene or 4-
Methyl-1-pentene itself can also be the reaction medium. The amount of the catalyst used is about 0.0001 to about 1.0 mmol of the component (a) in terms of titanium atom per component of the reaction volume, and the component (b) is the component (b) with respect to 1 mol of the titanium atom in the component (a). The amount of the metal atom in the component is about 1 to about 2000 mol, preferably about 5 to about 500 mol, and the component (c) is (c) per mol of the metal atom in the component (b).
The Si atom in the component is used in an amount of about 0.001 to about 10 moles, preferably about 0.01 to about 2 moles, particularly preferably about 0.05 to about 1 mole.

These catalyst components (a), (b) and (c) may be brought into contact with each other during the polymerization or may be brought into contact before the polymerization. In the contact before the polymerization, only two arbitrary ones may be freely selected and brought into contact with each other, or a part of each component may be contacted with two or three persons. Further, the contact between the respective components before the polymerization may be carried out in an inert gas atmosphere or in a 4-methyl-1-pentene or styrene atmosphere.

The polymerization temperature can be appropriately selected and is preferably about 0 to about 20.
The temperature is 0 ° C, more preferably about 20 to about 180 ° C. The pressure can be appropriately selected, and the reaction is from atmospheric pressure to about 100 kg / c.
It is preferable to carry out under the condition of m ³ .

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.
It is most effective to add hydrogen into the polymerization system.

The 4-methyl-1-pentene random copolymer of the present invention can be used to produce pipes, films, seals, hollow containers, and other various products by any molding method such as extrusion molding, hollow molding, injection molding, press molding, and vacuum molding. It can be molded into various shapes and supplied for various purposes.

When molding, various stabilizers, antioxidants, UV absorbers,
Antistatic agents, lubricants, plasticizers, pigments, inorganic or organic fillers can be added. Examples of these are 2,6
-Di-tert-butyl-p-cresol, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 4,4'-butylidene bis (6-tert-butyl) -M-cresol), tocopherols, ascorbic acid, dilaurylthiodipropionate, phosphoric acid stabilizer, fatty acid monoglyceride, N, N- (bis-2-hydroxyethyl) alkylamine, 1- (2'-hydroxy -3 ', 5'-di-tert-
(Butylphenyl) -5-chlorobenzotriazole, calcium stearate, magnesium oxide, magnesium hydroxide, alumina, aluminum hydroxide, silica, hydrotalcite, talc, clay, gypsum, glass fiber, titania, calcium carbonate, carbon black, petroleum resin , Polybutene, wax, synthetic or natural rubber and the like.

The 4-methyl-1-pentene random copolymer of the present invention can also be used as a mixture with another thermoplastic resin. Examples of these are high density, medium density or low density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / vinyl acetate copolymer, Surlyn A, ethylene / vinyl alcohol copolymer. Examples thereof include coalesce, polystyrene, and maleic anhydride graft products thereof.

Hereinafter, the present invention will be specifically described with reference to examples.

Example 1 (Preparation of highly active titanium catalyst component) 7.14 g (75 mmol) anhydrous magnesium chloride, 37 ml decane (2
25 mmol) is heated at 130 ° C. for 2 hours to form a uniform solution, and 1.67 g (11.3 mmol) of phthalic anhydride is added to this solution, and the mixture is stirred and mixed at 130 ° C. for another hour. Are dissolved in the homogeneous solution. The homogeneous solution thus obtained is cooled to room temperature and then added dropwise to 200 ml (1.8 mmol) of titanium tetrachloride kept at -20 ° C over 1 hour. After the completion of charging, the temperature of this mixed solution is raised to 110 ° C. over 4 hours, and when reaching 110 ° C., 18.8 mmol of diisobutyl phthalate is added, whereby the mixture is maintained at the same temperature for 2 hours with stirring. After the completion of the reaction for 2 hours, the solid portion was collected by heating, the solid portion was resuspended in 275 ml of TiCl ₄ , and then the reaction was conducted again at 110 ° C. for 2 hours. After completion of the reaction, the solid portion is again collected by heating, and washed thoroughly with decane at 110 ° C. and decane at room temperature until no free titanium compound is detected in the washing liquid. The titanium contact component synthesized by the above production method is retained as a decane slurry, and a part of this is dried for the purpose of examining the catalyst composition. The composition of the titanium catalyst component thus obtained was 2.1% by weight titanium, 58.0% by weight chlorine, 18.0% magnesium.
% By weight and 12.7% by weight of diisobutyl phthalate. The specific surface area was 210 m ² / g. The titanium catalyst component has an average particle size of 13μ and a geometric standard deviation (σg) of particle size distribution of 1.2.
It was a granular catalyst.

(Polymerization) The glass flask of 1 is thoroughly replaced with nitrogen. 200 ml of n-decane, 40 ml of styrene and 60 ml of 4-methyl-1-pentene are added to the system. Hydrogen 1 / hr and nitrogen 9
While flowing / hr, 1.5 mmol of triisobutylaluminum, 0.3 mmol of trimethylmethoxysilane and 0.12 mg atom of the above Ti catalyst component in terms of Ti atom were added at 50 ° C., and polymerization was carried out at 50 ° C. for 10 minutes. The yield of the obtained copolymer was 20 g, its styrene content was 16.3 mol%, and [η] was 4.
23 dl / g and w / n were 6.5. The styrene content in the n-heptane extract was 48.2 mol%.

The glass flask of Example 22 is thoroughly purged with nitrogen. In a flask, 400 ml of styrene and 4-methyl-1-pentene 3
Add 00 ml. Hydrogen 1 / hr and nitrogen 9 / hr
While flowing, 50 mmol of tri-n-hexylaluminum (6 mmol), trimethylmethoxysilane (0.6 mmol) and the Ti catalyst component of Example 1 (0.06 mg atom in terms of Ti atom) are added. Polymerization was carried out at 50 ° C for 1.5 hours. The yield of the obtained copolymer was 15 g, its styrene content was 27.3 mol%, and [η] was
5.32 dl / g and w / n were 6.1. The styrene content in the n-heptane extract was 78.3 mol%.

Example 3 In Example 1, 40 ml of styrene was added to 70 ml of 4-methyl-
Polymerization was carried out under the same conditions as in Example 1 except that 60 ml of 1-pentene was changed to 30 ml. The yield of the obtained copolymer is 16
g, its styrene content is 43.4 mol%, [η] is 2.37 dl / g,
The w / n was 6.4. The styrene content in the n-heptane extract was 88.7 mol%.

Comparative Example 11 The glass flask of 1 is thoroughly replaced with nitrogen. styrene
200 ml and 200 ml of 4-methyl-1-pentene are added into the system. At 50 ° C, 4 mmol of triisobutylaluminum and 1 mmol of titanium trichloride AA (TAC-141 manufactured by Toho Titanium Co., Ltd.) were added, and polymerization was carried out at 50 ° C for 10 minutes. The yield of the obtained copolymer was 7.3 g, the styrene content was 28.5 mol%, [η]
Was 2.49 dl / g and w / n was 16.8. The styrene content in the n-heptane-soluble part was 18.3 mol.

Example 4 1 kg of the copolymer synthesized according to Example 3 was added with tetrakis [methylene-3- (3 ', 5'-ditertiarybutyl-4'].
-Hydroxyphenyl) propionate] methane 0.10% by weight, 2,6-di-tert-butyl valarcresol 0.10% by weight
And add 0.10% by weight of calcium stearate, 26
After pelletizing at 0 degreeC, it shape | molded at 260 degreeC.

FM is 28,000kg / cm ² , Izod impact strength is 5.5kg ・ cm / cm
Met. The pencil hardness of the surface of the molded product was F.
That is, the present copolymer has high surface hardness and rigidity,
Suitable for use as a housing material.

〔The invention's effect〕

The present invention makes it possible to obtain a 4-methyl-1-pentene random copolymer excellent in heat resistance and rigidity and hardness, unlike the conventional olefin random copolymer.

The 4-methyl-1-pentene random copolymer of the present invention is an olefin polymer or copolymer such as polyethylene or polypropylene, or polystyrene, ABS resin, P
It can be used as a modifier of a polymer having an aromatic ring such as PO.

Furthermore, the 4-methyl-1-pentene random copolymer of the present invention can be used as a compatibilizing agent for a resin mixture such as a mixture of polyolefin and polystyrene.

[Brief description of drawings]

FIG. 1 is a flow chart showing the steps for preparing the catalyst according to the present invention.

Claims (2)

[Claims] 1. A 4-methyl-1 comprising a styrene component unit (A) and a 4-methyl-1-pentene component unit (B).
A pentene random copolymer, wherein (i) the styrene component unit (A) is in the range of 10 to 90 mol% and the 4-methyl-1-pentene component unit (B) is in the range of 10 to 90 mol%, (Ii) the intrinsic viscosity measured in decalin at 135 ° C. is in the range of 0.5 to 20 dl / g, (iii) the molecular weight distribution (w / n) measured by gel permeation chromatography is 10 or less, (Iv) Ratio of the content (a ₁ ) of the styrene component unit in the boiling n-heptane-soluble content of the copolymer (a ₁ / to the content (a ₀ ) of the styrene component unit in the copolymer) a ₀ ) is 0.8
The above is the 4-methyl-1-pentene random copolymer characterized by the above. 2. (a) Magnesium compound, general formula Ti
(OR) gX _4- g (R is a hydrocarbon group, X is a halogen, 0≤g
Magnesium formed by reacting a tetravalent titanium compound represented by ≦ 4), a diester and optionally a halogen compound (which is not always necessary when the magnesium compound or the titanium compound contains a halogen atom). A highly active titanium catalyst component containing titanium, halogen, and a diester as essential components, (b) an organoaluminum compound catalyst component, and (c) an organosilicon compound catalyst component having a Si—O—C bond. By copolymerizing styrene and 4-methyl-1-pentene in the presence of 10 to 90 mol% of styrene component unit (A) and 4-methyl-pentene.
The 1-pentene component unit (B) is in the range of 10 to 90 mol%, the intrinsic viscosity measured in decalin at 135 ° C. is in the range of 0.5 to 20 dl / g, and measured by gel permeation chromatography. The molecular weight distribution (w / n) is 10 or less, and the content of the styrene component unit in the boiling n-heptane-soluble component of the copolymer with respect to the content (a ₀ ) of the styrene component unit in the copolymer the ratio (a ₁ / a ₀₎ of the (a ₁₎ is 0.8
A method for producing a 4-methyl-1-pentene random copolymer as described above.