JP3186218B2 - Terminal vinyl ethylene-propylene copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl ethylene-propylene copolymer which can be used as a macromonomer and a method for producing the same. Also, the present invention relates to a copolymer of a terminal vinyl ethylene-propylene copolymer and an α-olefin in which the compatibility of the poly (α-olefin) is modified and a method for producing the same.

[0002]

2. Description of the Related Art Generally, a polymer having a terminal polymerizable group (macromonomer) requires synthesis of styrenes and dienes under special conditions such as low-temperature anionic polymerization. Α-olefin macromonomers cannot be synthesized by such a technique.

[0003] If the molecular terminal is a vinyl type, its polymerizability is enhanced, and its utility as a macromonomer is improved.
From such a viewpoint, various methods for producing a vinyl-terminated copolymer have been proposed. That is, JP-A-1-207248 discloses a method for producing a terminal vinyl oligomer using an aluminoxane-based compound as a catalyst, and JP-A-1-203410 discloses a method for producing an oligomer by copolymerizing ethylene and an α-olefin. It is proposed in the gazette.

[0004]

However, in the former case of the prior art, the degree of polymerization of the obtained oligomer is as low as about a number, so that it is not always satisfactory as a macromonomer. Also, the terminal of the obtained oligomer is a vinylidene group or a hydrogenated product thereof, which has a problem that it is not practical because of limited polymerizability.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an ethylene-propylene copolymer having a large composition ratio of a vinyl group at a molecular terminal and capable of sufficiently exerting a function as a macromonomer, and an ethylene-propylene copolymer thereof. It is intended to provide a manufacturing method. Also, a copolymer of a vinyl-terminated ethylene-propylene copolymer and an α-olefin, which improves the compatibility of poly (α-olefin) and is useful as a compatibilizer for a poly (α-olefin) composition, and its production It is another object to provide a method.

[0006]

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides an ethylene-propylene copolymer having a vinyl group at a molecular terminal, wherein a vinyl group and a vinylidene group existing at the molecular terminal are present. The composition ratio is 6: 1 or more, preferably 9: 1 or more, and the number average molecular weight (M
n) having a terminal vinyl ethylene-propylene copolymer of 500 or more, and the following general formula (I):

Embedded image (Wherein m and n represent an integer of 2 or more), and the ratio of repeating units m and n is m + n = 100%, and the following formula ( (II) and (III): Provided is a vinyl ethylene-propylene copolymer having a range of 0.1 ≦ n ≦ 50 (II) 50 ≦ m ≦ 99.9 (III). Further, the terminal vinyl ethylene-propylene copolymer preferably has a weight average molecular weight (Mw).
/ Number average molecular weight (Mn) is 7 or less, more preferably,
3 or less.

Further, ethylene and propylene are copolymerized by using a catalyst containing the following compounds (A), (B) and (C) as main components, and an ethylene-propylene copolymer having a vinyl group at a molecular terminal is provided. Wherein the composition ratio of vinyl groups and vinylidene groups present at the molecular terminals is 6: 1 or more, and the number average molecular weight (Mn) is 500
The present invention provides a method for producing a terminal vinyl ethylene-propylene copolymer. (A) The following general formula (IV): (R ₅ C ₅ ) ₂ · M · X ₂ (IV) (where R ₅ C ₅ is a hydrocarbon-substituted cyclopentadienyl group, and R is 1 carbon atom) To 20 alkyl groups, aryl groups, alkylaryl groups, or arylalkyl groups, M is a zirconium atom or a hafnium atom, X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an alkylaryl group. , or arylalkyl group or an alkoxy group having a carbon 1 to 20, an aryloxy group, alkylaryl group or an arylalkoxy group .5 amino represented by R is .2 pieces which may be the same or different R _5, C ₅ may be the same or different, and two Xs may be the same or different, and may have a crosslinked structure. (B) a compound which reacts with a transition metal compound to form an ionic complex and / or an aluminoxane. (C) an organoaluminum compound. Further, the use ratio of the ethylene and propylene is 0.1%.
The present invention provides a method for producing a vinyl ethylene-propylene copolymer having a ratio of 5: 1 to 5: 1, preferably 1: 1 to 3: 1. Here, the ratio of ethylene and propylene to be used within the above-mentioned range is such that if the ratio is 5: 1 or more, the content of ethylene is too large to increase the molecular weight, and the ratio of 0.
If the ratio is 5: 1 or less, the propylene content becomes too large, resulting in a low molecular weight, which is not suitable as a macromonomer. Further, the present invention provides a method for producing a terminal vinylethylene-propylene copolymer, wherein the compound (B) is a compound having a cation and an anion having a plurality of groups bonded to elements.

The above-mentioned vinyl ethylene-propylene copolymer and the following general formula (V): R—CH ＝ CH ₂ (V) (wherein R is a hydrogen atom, an alkyl having 1 to 20 carbon atoms) , An aryl group, an alkylaryl group, or an arylalkyl group, or a silicon-containing substituent having an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group having 1 to 20 carbon atoms) After isolating the copolymer with olefin and the ethylene-propylene copolymer having a vinyl-terminated terminal obtained by the above-mentioned production method, or in the reaction solution without isolation, the copolymerization is carried out in one step. Provided is a method for producing a copolymer of an ethylene-propylene copolymer having a terminal vinyl-containing compound and an α-olefin, which is obtained by copolymerizing the copolymer and the α-olefin.

[0009]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described more specifically. In the compound (A) used in the present invention,
In the above formula (IV), R is an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group, or an arylalkyl group, M is a zirconium atom or a hafnium atom, X is a hydrogen atom, a halogen atom, 20 alkyl groups,
An aryl group, an alkylaryl group, an arylalkyl group, or an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, an alkylaryloxy group, or an arylalkoxy group. Here, as the alkyl group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, hexyl group, heptyl group, octyl group, Nonyl, capryl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, eicosyl and the like. Carbon number 1
Examples of the 20 aryl groups and arylalkyl groups include a phenyl group, a benzyl group, and a phenethyl group. Examples of the alkylaryl group having 1 to 20 carbon atoms include a p-tolyl group and a pn-butylphenyl group. Examples of the alkoxy group having 1 to 20 carbon atoms, aryloxy group, alkylaryloxy group, and arylalkoxy group include methoxy, ethoxy, propoxy, phenoxy, p-tolyloxy, and benzyloxy groups. Can be.

Specific examples of the compound of formula (IV) include, for example, [(CH ₃ ) ₅ C ₅ ] ₂ Hf (CH ₂ Ph) ₂ , [(CH
_{3) 5 C 5] 2 Zr} (CH 2 Ph) 2, [(CH 3) 5 C 5] H
fPh ₃ , [(CH ₃ ) ₅ C ₅ ] ZrPh ₃ , [(CH ₃ ) _{5
C 5] 2 Hf (C 6} H 4 -p-CH 3) 2, [(CH 3)
_{5 C 5] 2 Zr (C} 6 H 4 -p-CH 3) 2, [(CH 3)
_{5 C 5] 2 Hf (CH} 3) 2, [(CH 3) 5 C 5] 2 Zr (C
_{H 3) 2, [(C} 2 H 5) 5 C 5] 2 Hf (CH 3) 2, [(C 2
_{H 5) 5 C 5] 2} Zr (CH 3) 2, [(nC 3 H 7) 5 C 5] 2
Hf (CH ₃ ) ₂ , [(nC ₃ H ₇ ) ₅ C ₅ ] ₂ Zr (CH ₃ )
₂ , [(CH ₃ ) ₅ C ₅ ] ₂ HfH (CH ₃ ), [(CH ₃ ) _{5
C 5] 2 ZrH (CH 3} ), [(C 2 H 5) 5 C 5] 2 HfH
(CH ₃ ), [(C ₂ H ₅ ) ₅ C ₅ ] ₂ ZrH (CH ₃ ),
[(C ₃ H ₇ ) ₅ C ₅ ] ₂ HfH (CH ₃ ), [(C ₃ H ₇ ) _{5
C 5] 2 ZrH (CH 3} ), [(CH 3) 5 C 5] 2 Hf
(H) ₂ , [(CH ₃ ) ₅ C ₅ ] ₂ Zr (H) ₂ , [(C
_{2 H 5) (CH 3)} 4 C 5] 2 Hf (CH 3) 2, [(C 2 H 5)
(CH ₃ ) ₄ C ₅ ] ₂ Zr (CH ₃ ) ₂ , [(nC ₃ H ₇ ) (C
_{H 3) 4 C 5] 2} Hf (CH 3) 2, [(nC 3 H 7) (C
_{H 3) 4 C 5] 2} Zr (CH 3) 2, [(nC 4 H 9) (C
_{H 3) 4 C 5] 2} Hf (CH 3) 2, [(nC 4 H 9) (C
_{H 3) 4 C 5] 2} Zr (CH 3) 2, [(CH 3) 5 C 5] 2 Hf
Cl ₂ , [(CH ₃ ) ₅ C ₅ ] ₂ ZrCl ₂ , [(CH ₃ ) ₅ C
₅ ] ₂ HfH (Cl), [(CH ₃ ) ₅ C ₅ ] ₂ ZrH (C
l), [(CH ₃ ) ₅ C ₅ ] ₂ Hf (OCH ₃ ) ₂ , [(CH
_{3) 5 C 5] 2 Zr} (OCH 3) 2, [(CH 3) 5 C 5] 2 Hf
(OCH ₂ Ph) ₂ , [(CH ₃ ) ₅ C ₅ ] ₂ Zr (OCH ₂
Ph) ₂ , etc. can be suitably used, and among them,

[(CH ₃ ) ₅ C ₅ ] ₂ Hf (CH ₂ Ph) ₂ ,
[(CH ₃ ) ₅ C ₅ ] ₂ Zr (CH ₂ Ph) ₂ , [(CH ₃ ) _{5
C 5] 2 Hf (CH 3} ) 2, [(CH 3) 5 C 5] 2 Zr (CH
₃ ) ₂ , [(CH ₃ ) ₅ C ₅ ] ₂ HfH (CH ₃ ), [(C
_{H 3) 5 C 5] 2} ZrH (CH 3), [(CH 3) 5 C 5] 2 H
f (H) ₂ , [(CH ₃ ) ₅ C ₅ ] ₂ Zr (H) ₂ , [(C _{2
H 5) (CH 3) 4} C 5] 2 Hf (CH 3) 2, [(C 2 H 5)
(CH ₃ ) ₄ C ₅ ] ₂ Zr (CH ₃ ) ₂ , [(nC ₃ H ₇ ) (C
_{H 3) 4 C 5] 2} Hf (CH 3) 2, [(nC 3 H 7) (C
_{H 3) 4 C 5] 2} Zr (CH 3) 2, [(nC 4 H 9) (C
_{H 3) 4 C 5] 2} Hf (CH 3) 2, [(nC 4 H 9) (C
_{H 3) 4 C 5] 2} Zr (CH 3) 2, pentaalkyl cyclopentadienyl compounds are preferred, such as, in particular hafnium compound is preferred. The compound of the formula (IV) can be used alone or in combination of two or more.

As the compound (B) used in the present invention, any compound which reacts with a transition metal compound to form an ionic complex can be used. As such a compound, for example, a compound comprising a cation and an anion in which a plurality of groups are bonded to an element, that is, the compound (B) is a group IIIB, IVB, VB
, VIB, VIIB, VIII, IA, IB, IIA, IIB
Cation containing an element selected from group IVA, group IVA and group VIIA, and a plurality of groups are group VB, group VIB, group VIIB, group VIII of the periodic table
Preferable examples include a compound comprising an anion bonded to an element selected from Group IV, Group IB, Group IIB, Group IIIA, Group IVA and Group VA, particularly a coordination complex compound.

As the compound (B), the following formulas (VI) and (VI)
The compound represented by (I) or (VIII) can be suitably used. ([L ¹ -H] ^{g +} ) _h ([M ² X ¹ X ² ... X ⁿ ] ^(nm)- ) _i (VI) ([L ² ] ^{g +} ) _h ([M ³ X ¹ X ^{2 ... X n] (nm) -} ) i ··· (VII) ( where, L ² is ^{M 4, R 2 R 3 M} 5 or _{^{R 4 3 C) ([L}} 1 -Z] g +) h ( [M ² X ¹ X ² ... X ⁿ ] ^(nm)- ) _i (VIII) [In the formulas (VI), (VII) and (VIII), L ¹ is a Lewis base, Z is an alkyl group, aryl group, an arylalkyl group, a hydrocarbon group, VB group of M ² and M ³ are each the periodic table such as an alkyl aryl group, VIB group, VIIB group, VIII group, IB, IIB,
An element selected from the group IIIA, IVA and VA, M ⁴ is a transition metal, preferably a metal selected from the group IB, IIB and VIII of the periodic table, and M ⁵ is selected from a group VIII of the periodic table metal, X ¹ to X ⁿ are each a hydrogen atom, dialkylamino group, alkoxy group, aryl group, substituted aryl group, an aryloxy group, an alkyl group, a substituted alkyl group, organometalloid group or halogen atom, R ² and R ³ represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ⁴ represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an arylalkyl group, a substituted arylalkyl group, and an alkylaryl. Or a substituted alkylaryl group, each R ⁴
May be the same or different. m is a valence of M ² or M ³ and is an integer of 1 to 7, n is an integer of 2 to 8, g is L ¹ -H,
L ^{2 is} an ionic valence of 1 to 7; h is an integer of 1 or more;
i = (h × g) / (nm). ]

Specific examples of the above Lewis base include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, dimethylaniline and pyridine. , 2-cyanopyridine, 3-cyanopyridine, 4-cyanopyridine, triethylamine, 2,2-
Examples include amines such as bipyridine and phenanthroline, and phosphines such as triethylphosphine and triphenylphosphine. Specific examples of Z include a methyl group,
Examples include an ethyl group, a benzyl group, and a trityl group. M
Examples ² and ^{M 3, B, Al, Si} , P, A
s, Sb, etc. Specific examples of ^{M 4,} Ag, Cu or the like, M
Specific examples of ⁵ include Fe, Co, Ni and the like. Specific examples of X ^{1 to} X ⁿ include, for example, a dimethylamino group, a diethylamino group as a dialkylamino group;
A methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group; a phenyl group, a 4-tolyl group, a 3,5-xylyl group, a benzyl group as an aryl group or a substituted aryl group;
Those having 6 to 20 carbon atoms such as a pentafluorophenyl group, a 3,5-bis (trifluoromethyl) phenyl group and a 4-tert-butylphenyl group; a phenoxy group, a 2,6-dimethylphenoxy group as an aryloxy group, Naphthyloxy group; methyl group, ethyl group,
n-propyl group, iso-propyl group, n-butyl group,
1 to 1 carbon atoms such as n-octyl group and 2-ethylhexyl group
20; a pentamethylantimony group, a trimethylsilyl group, and a trimethylstannyl group as organic metalloid groups; and F, Cl, Br, and I as halogens. Specific examples of the substituted cyclopentadienyl group for R ² and R ³ include a methylcyclopentadienyl group, a butylcyclopentadienyl group, a pentamethylcyclopentadienyl group, a trifluoromethyltetramethylcyclopentadienyl group Nitrocyclopentadienyl group, ethoxycarbonylcyclopentadienyl group, cyanocyclopentadienyl group and the like. Specific examples of R ⁴ include:
Methyl group, ethyl group, phenyl group, p-tolyl group, p-
Examples include a methoxyphenyl group and a p-dimethylaminophenyl group.

Among the compounds of the above formulas (VI), (VII) and (VIII), the following compounds can be used particularly preferably. Compound of formula (VI): trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, dimethylanilinium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, Trikis (pentafluorophenyl) borate tri (n-
Butyl) ammonium, triethylammonium hexafluoroarsenate,

Compound of formula (VII) Ferrocenium tetraphenylborate, trityl tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, methylferrocenium tetrakis (pentafluorophenyl) borate, decamethylferrotetrakis (pentafluorophenyl) borate Cerium, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluoroarsenate, silver hexafluoroantimonate,

Compound of formula (VIII) Tetrakis (pentafluorophenyl) borate (N-benzyl-2-cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-benzyl-3-cyanopyridinium), tetrakis (pentafluorophenyl) ) Boric acid (N-benzyl-4-cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methyl-2-cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methyl-3-cyanopyridinium), tetrakis (N-methyl-4-cyanopyridinium) borate (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, trimethyl tetrakis (pentafluorophenyl) borate (m-trifluoromethylphenyl) Ammonium tetrakis (pentafluorophenyl) borate benzyl pyridinium,

The aluminoxane used as the component (B) of the catalyst in the present invention is not particularly limited, and after the contact reaction between the organoaluminum and a condensing agent such as a hydrate compound, the solid residue is filtered off, and the filtrate is subjected to normal pressure or reduced pressure. Below 30-2
At a temperature of 00 ° C, preferably 40-150 ° C,
It is preferable that the composition is heat-treated while evaporating the solvent for 0 minute to 8 hours, preferably 30 minutes to 5 hours. In this heat treatment, the temperature may be appropriately determined depending on various conditions, but is usually in the above range. Generally, at a temperature lower than 30 ° C., no effect is exhibited, and at a temperature higher than 200 ° C., thermal decomposition of the alkylaluminoxane itself occurs, and both are not preferred. Depending on the processing conditions of the heat treatment, the reaction product is obtained in the form of a colorless solid or solution. The product thus obtained can be dissolved or diluted with a hydrocarbon solvent, if necessary, and used as a catalyst solution. A preferred example of the contact product between the organoaluminum used as the catalyst (B) component and the condensing agent, particularly a preferred example of the alkylaluminoxane is an aluminum-methyl group observed by proton nuclear magnetic resonance spectrum ( ¹ H-NMR). (Al-CH ₃₎ high magnetic field component in the methyl proton signal region based on the binding is of 50% or less. In other words, at room temperature of the above contact product, when observing the proton nuclear magnetic resonance ⁽¹ H-NMR) spectra in toluene solvent, methyl proton signal based on the Al-CH ₃ in tetramethylsilane (TMS) standard 1 .0
It is found in the range of -0.5 ppm. Because TMS proton signals (0 ppm) is in the methyl protons observation area based on the Al-CH _3, methyl proton signal based on the Al-CH _3, it was measured based on the methyl proton signal 2.35ppm toluene in TMS standard When divided into a high magnetic field component (i.e., -0.1 to -0.5 ppm) and another magnetic field component (i.e., 1.0 to -0.1 ppm), the high magnetic field component is 50% or less of the whole. , Preferably 45-5%. The organoaluminum compound as the component (C) is not particularly limited, and examples thereof include compounds represented by the following formula (IX). AlR ⁵ ₃ ··· (IX) (wherein, R ⁵ is a hydrogen atom, 1 to halogen atoms or carbon atoms
8 represents an alkyl group. Specifically, triisobutylaluminum, diisobutylaluminum hydride, trimethylaluminum, triethylaluminum, diethylaluminum chloride and the like can be particularly preferably used.

The catalyst used in the present invention comprises the above components (A),
(B) and (C). In this case, the use conditions of these components are not particularly limited. However, when the component (B) is a compound which reacts with a transition metal compound to form an ion-generating complex, the use ratio of the component (A): the component (B) (Molar ratio) is 1: 0.1 to 1: 100, particularly 1: 0.5 to 1:
10, especially 1: 0.8 to 1: 5. When the component (B) is aluminoxane, the component (A)
The use ratio of component: (B) component (calculated as aluminum atom) is from 1: 1 to 1:10 ⁶ , particularly from 1:10 to 1:10 ^3.
It is preferable that The usage of the component (A) and the component (B) is not limited. For example, the component (A) and the component (B)
The components may be brought into contact in advance and the reactants may be separated and washed before use, or the components (A) and (B) may be added simultaneously or separately to the polymerization system.

The amount of the component (C) used is 1 to 1000, particularly 10 to 10 as a molar ratio of the component (C) / the component (A).
700, especially preferably 20 to 500.
The manner of using the component (C) is not limited. For example, (A)
The contact product between the component and the component (B) and the component (C) are added to the polymerization system, or the contact product between the component (A) and the component (C) and the component (B) are added to the polymerization system. , (A) component,
The component (B) and the component (C) can be added to the polymerization system simultaneously or separately.

In the copolymerization reaction of ethylene and propylene, the reaction temperature is not particularly limited.
° C, preferably 20-80 ° C. The pressure can be set arbitrarily. For example, the low polymerization reaction can be carried out at a low pressure of 10 kg / cm ² G or less, or at normal pressure if desired. To further explain the reaction temperature, when the reaction temperature is low, a product having a high degree of polymerization is easily produced, and when the reaction temperature is high, a product having a low degree of polymerization is obtained. May be appropriately determined. However, if the temperature is outside the range of 0 to 100 ° C., the activity of the catalyst may decrease.

In the copolymerization reaction of ethylene and propylene, a solvent can be used. Examples of the solvent include aromatic carbons such as benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, naphthalene, tetralin, butylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene, dipentylbezen, dodecylbenzene, and biphenyl. Hydrogen; 2-methylbutane, hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2,2,3-trimethylpentane, isooctane, nonane, 2,2,5- Aliphatic hydrocarbons such as trimethylhexane, decane and dodecane; other cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane,
Alicyclic hydrocarbons such as decalin; petroleum ether, petroleum benzine, petroleum naphtha, ligroin, industrial gasoline, kerosene; and polar group-containing solvents such as chlorobenzene, phenylmethyl ether, dimethylaniline, and phenylmethylthioether.

The polymerization method may be any of a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like, but a solution polymerization method is preferred from the viewpoint of catalytic activity.

According to the process for producing a copolymer of ethylene and propylene of the present invention, the following general formula (X)

Embedded image (Wherein m and n are integers of 2 or more.) A copolymer of ethylene and propylene having a vinyl group at the molecular terminal represented by the formula can be obtained with high selectivity under simple and mild conditions.

According to further studies by the present inventors, when ethylene and propylene are copolymerized, hydrogen may be present under the above reaction conditions. Although the amount of hydrogen used is arbitrary, it is generally 1 to 100 mol%, preferably 5 to 20 mol%, based on the starting propylene.

Ethylene obtained by the method of the present invention
The composition ratio of the propylene copolymer can be variously adjusted depending on the use ratio of ethylene and propylene to be used, reaction conditions, and the like.

The α-olefin used in the present invention is
Specifically, ethylene, propylene, 1-butene, 1-
Pentene, 1-hexene, 1-octene, 4-methyl-
Examples thereof include 1-pentene, styrene, vinyltrimethylsilane, allyltrimethylsilane, and allyltriphenylsilane.

The reaction temperature for the copolymerization of a vinyl ethylene-propylene copolymer with an α-olefin is not particularly limited, but is usually 0 ° C. to 200 ° C.
20 ° C to 150 ° C is preferred. Any reaction pressure can be selected.

Examples of the solvent include aromatic hydrocarbons such as benzene, xylene, toluene, ethylbenzene, cumene, mesitylene, naphthalene, tetralin, butylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene, dipentylbenzene, dodecylbenzene and biphenyl. Hydrogen; 2-methylbutane, hexane,
2-methylpentane, 2,2-dimethylbutane, 2,3
-Dimethylbutane, heptane, octane, 2,2,3-
Trimethylpentane, isooctane, nonane, 2,2
Aliphatic hydrocarbons such as 5-trimethylhexane, decane and dodecane; other alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, citarohexane, methylcyclohexane, ethylcyclohexane and decalin; petroleum ether, petroleum benzene, petroleum naphtha, ligroin And industrial gasoline, kerosene; and solvents containing polar groups such as chlorobenzene, phenylmethyl ether, dimethylaniline, and phenylmethylthioether.

The polymerization method may be any of a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like, but a solution polymerization method is preferred from the viewpoint of catalytic activity.

The composition ratio (molar ratio) between the terminal vinyl ethylene-propylene copolymer and the α-olefin is usually from 1:50 to 1: 5000, from 1: 100 to 1: 100.
0 is preferred. If the ratio is 1:50 or more, the original properties of poly (α-olefin) are impaired, and if the ratio is 1: 5000 or less, the grafting efficiency is low, and the compatibility is not improved.

Further, with respect to the synthesis of a vinyl ethylene-propylene copolymer and a copolymer with an α-olefin, a method in which the vinyl ethylene-propylene copolymer is isolated and then copolymerized with an α-olefin, or A method of copolymerizing an ethylene-propylene copolymer and an α-olefin in one step in a reaction solution without isolation (2)
Step polymerization method) may be used.

[0033]

The present invention will be described in more detail with reference to the following examples. 1. Synthesis of Vinyl Ethylene-Propylene Terminal Copolymer Example 1 400 ml of a solvent toluene and 2 mmol of triisobutylaluminum were added to an autoclave having an internal volume of 1 liter in an argon stream, and the temperature was raised to 50 ° C. Subsequently, propylene 3 kg / cm ² , ethylene 6 kg / cm ^2
Then, a toluene solution (10 ml) of 2 mmol of methylaluminoxane and 0.01 mmol of bispentamethylcyclopentadienyl hafnium dichloride prepared in advance was mixed. Reaction pressure 9Kg / c
supply of ethylene so that m ^{2 is} constant;
A minute reaction was allowed. 159 g of an ethylene-propylene copolymer was obtained.

90 MHz-1H-N of the obtained copolymer
As a result of measuring MR (deuterated chloroform solvent, tetramethylsilane 0.00 ppm standard), δ4.60-4.75
In the vicinity, there is a peak based on terminal vinylidene and δ4.
Peaks based on terminal vinyl were observed at around 80 to 5.15 and δ 5.50 to 6.10, and the ratio (molar ratio) was vinyl / vinylidene = 95/5. In addition, in the infrared absorption spectrum (IR), 1640, 984, 904
At cm ⁻¹ , an absorption peak of terminal vinyl was remarkably observed. From GPC, the number average molecular weight (Mn) = 90
0, weight average molecular weight (Mw) = 13,200.
The GPC measurement was carried out using an apparatus: Waters ALC / G
PC 150C, column: Tosoh (product) TSK HM
+ GMH6 × 2, solvent: 1,2,4-trichlorobenzene, temperature: 135 ° C., flow rate: 1 ml / min, polyethylene conversion. The propylene content (molar ratio)
Was 22 mol% by NMR.

Example 2 An autoclave having an internal volume of 1 liter was charged with 400 ml of the solvent toluene, 2 mmol of triisobutylaluminum, 2 mmol of methylaluminoxane and 0.01 mmol of bispentamethylcyclopentadienylhafnium dichloride under an argon stream at 50 ° C. The temperature rose. Subsequently, assuming a propylene partial pressure of 3 kg / cm ² and an ethylene partial pressure of 6 kg / cm ² (total pressure of 9 kg / cm ² ),
Ethylene was reacted by continuously supplying ethylene for 30 minutes so that the total pressure was constant at 9 kg / cm ² . 132 g of an ethylene-propylene copolymer were obtained. Terminal vinyl / vinylidene terminal = 96/4, Mn = 4,200, Mw = 8.6
00, the propylene content was 29 mol%.

Example 3 Example 3 was carried out in the same manner as in Example 1 except that the main catalyst was changed to bispentamethylcyclopentadienyl zirconium dichloride. 84 g of an ethylene-propylene copolymer was obtained. Terminal vinyl / vinylidene terminal = 90/10, M
n = 2,400, Mw = 27,200, and propylene content was 11 mol%.

Example 4 The procedure of Example 1 was repeated, except that 0.01 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate was used in place of methylaluminoxane. 165 g of an ethylene-propylene copolymer was obtained. Terminal vinyl / terminal vinylidene = 95/5, M
n = 1,200, Mw = 16,400, and propylene content was 21 mol%.

Example 5 The procedure of Example 2 was repeated, except that 0.01 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate was used in place of methylaluminoxane. As a result, 151 g of an ethylene-propylene copolymer was obtained. Terminal vinyl / terminal vinylidene = 96/4, M
n = 4,400, Mw = 8,900, propylene content 2
8 mol%.

Example 6 The procedure of Example 3 was repeated, except that 0.01 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate was used instead of methylaluminoxane. 93 g of an ethylene-propylene copolymer was obtained. Terminal vinyl / vinylidene terminal = 90/10, M
n = 2,600, Mw = 25,100, and propylene content was 11 mol%.

[0040] 2. Terminal vinyl ethylene-propylene copolymer
Example 7 Synthesis of graft copolymer of union and α-olefin Example 7 In a 1-liter autoclave, a solvent of toluene / 400 ml, 2 mmol of triisobutylaluminum, dimethylanilinium tetrakis (pentafluorophenyl) borate was placed under an argon stream. 0.003 mmol, 0.003 mmol of bispentamethylcyclopentadienyl hafnium dichloride were charged, and the temperature was raised to 50 ° C. Subsequently, a propylene partial pressure of 3 kg / cm ² and an ethylene partial pressure of 6 kg / cm ² (total pressure of 9 kg / cm ² ) were continuously supplied for 10 minutes so that the total pressure of ethylene was constant at 9 kg / cm ^2. I let it. Unreacted ethylene and propylene were sufficiently removed from the reaction solution. Here, a part was extracted and the molecular weight was measured. As a result, Mn = 5,100,
Mw = 10,200 and the propylene content was 26
Mol%. Then, propylene was added at 9 kg / cm.
^{As a second step} , a continuous supply of 0.01 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate and 0.01 mmol of (ethylenebisindenyl) zirconium dichloride (in 10 ml of toluene) was added to the polymerization system for 1 hour, Reacted. 120 g of an isotactic (propylene-terminal vinyl ethylene / propylene copolymer) copolymer was obtained. This was subjected to Soxhlet extraction with a heptane solvent for 1 hour to remove unreacted terminal vinylethylene-propylene copolymer,
104 g remained as extraction residue. Its IR was measured to find that it was 1640,984,904 based on the terminal vinyl.
absorption of cm ^-1 is disappeared, also, absorption based on rolling methylene polyethylene backbone 720 cm ^-1 was confirmed. Also, the melting point was 138 ° C. by DSC, and GPC
Mn = 20,000 and Mw = 64,000 determined from the above. From the above, it is understood that the obtained copolymer is an isotactic (propylene-terminal vinylethylene / propylene copolymer) graft copolymer.

Further, in ¹³ C-NMR (solvent trichlorobenzene 80%, heavy benzene 20%, 130 ° C.)
The ethylene / propylene copolymer calculated from the intensity ratio of the peak of the side chain methyl group of the isotactic polyethylene at 1.3 ppm and the peak of the side chain methyl group of the ethylene / propylene copolymer at 19.4 to 20.2 ppm. The molar ratio of the polymer was 2%.

[0042] 3. Compatibility evaluation This isotactic (propylene-ethylene-propylene copolymer) copolymer (75% by weight) and an ethylene-vinyl acetate copolymer (8% by weight) having a vinyl acetate content of 8% were added and mixed. As a result of observing the dispersion state with a transmission electron microscope, it was found that good compatibility was exhibited.

COMPARATIVE EXAMPLE 1 In an autoclave having an internal volume of 1 liter, 400 ml of solvent toluene and 2 mmol of triisobutylaluminum were charged under an argon stream, and 9 kg / c of propylene was added.
m2, dimethylanilinium tetrakis (pentafluorophenyl) borate 0.0
1 mmol, (ethylenebisindenyl) zirconium dichloride 0.01 mmol mixed solution (toluene 10m
1) was added to the polymerization system and reacted for 1 hour. 141 g of isotactic polypropylene was obtained. Example 7
When the compatibility was observed in the same manner as in the above, the dispersibility was poor.

[0044]

As described above, the terminal vinyl ethylene-propylene copolymer according to the present invention contains a vinyl group at the molecular terminal at a ratio of 6: 1 or more to the vinylidene group, so that it can sufficiently exhibit its function as a macromonomer. . In addition, the production method can efficiently obtain a macromonomer having a high ratio of vinyl groups and excellent polymerization characteristics. Further, the copolymer of the copolymer and the α-olefin is modified in compatibility with poly (α-olefin) because the compatibility of poly (α-olefin) is modified. It has the effect of acting as a compatibilizer in mixing.

[Brief description of the drawings]

FIG. 1 is a flow chart showing a method for producing a terminal vinyl ethylene-propylene copolymer of the present invention.

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 C08F 10/00-10/14

Claims (8)

(57) [Claims] (1) ethylene having a vinyl group at a molecular terminal;
A propylene copolymer having a composition ratio of vinyl groups to vinylidene groups of 6: 1 or more and a number average molecular weight (Mn) of 500 or more, which is present at the molecular terminals. Ethylene-propylene copolymer. 2. The following general formula (I): The terminal vinyl ethylene-propylene copolymer according to claim 1, wherein m and n each represent an integer of 2 or more. 3. The ratio between the repeating units m and n is m
The terminal according to claim 2, wherein the following formulas (II) and (III) are within the range of 0.1 ≦ n ≦ 50 (II) 50 ≦ m ≦ 99.9 (III), where + n = 100%. Vinyl ethylene
Propylene copolymer. 4. The following compounds (A), (B) and (C)
Using a catalyst containing as a main component, ethylene and propylene copolymerized, characterized in that the ethylene-propylene copolymer having a vinyl group at the molecular end, the vinyl group present at the molecular end And a vinylidene group in a composition ratio of 6: 1 or more, and a number average molecular weight (M
A method for producing a vinyl ethylene-propylene copolymer having n) of 500 or more. (A) The following general formula (IV): (R ₅ C ₅ ) ₂ · M · X ₂ (IV) wherein R ₅ C ₅ is a hydrocarbon-substituted cyclopentadienyl group, and R is 1 carbon atom To 20 alkyl groups, aryl groups, alkylaryl groups, or arylalkyl groups, M is a zirconium atom or a hafnium atom, X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an alkylaryl group. Or an arylalkyl group, or an alkoxy group, an aryloxy group, an alkylaryloxy group, or an arylalkoxy group having 1 to 20 carbon atoms, wherein 5 Rs may be the same or different, and 2 R ₅ C ₅ may be the same or different.
Two Xs may be the same or different, and may have a crosslinked structure. A) a transition metal compound represented by the formula: (B) a compound which reacts with a transition metal compound to form an ionic complex and / or an aluminoxane. (C) an organoaluminum compound. 5. The method according to claim 4, wherein the ratio of ethylene to propylene is in the range of 0.5: 1 to 5: 1. 6. The method according to claim 4, wherein said compound (B) is a compound having a cation and an anion in which a plurality of groups are bonded to an element. 7. A terminal vinyl ethylene-propylene copolymer according to any one of claims 1 to 3, and the following general formula:
(V): R—CH ＝ CH ₂ (V) (wherein R is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group, or an arylalkyl group, or a 1 to 1 carbon atom) 20 with an α-olefin represented by the formula (20): an alkyl group, an aryl group, an alkylaryl group or a silicon-containing substituent having an arylalkyl group). 8. After isolating the vinyl-terminated ethylene-propylene copolymer obtained by the production method according to any one of claims 4 to 6, or in the reaction solution without isolation, A method for producing a copolymer of a vinyl-terminated ethylene-propylene copolymer and an α-olefin in which the copolymer and the α-olefin are copolymerized in one step.