JP3255938B2 - Epoxy group-containing polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[Background of the Invention]

BACKGROUND OF THE INVENTION The present invention relates to an adhesive property, a printability, and an adhesive property obtained by introducing an epoxy group into a specific α-olefin polymer having an olefinically unsaturated bond at a terminal.
The present invention relates to an epoxy group-containing polymer having excellent compatibility in a polymer blend.

[0002]

2. Description of the Related Art α-olefin homopolymers and copolymers are not only inexpensive, but also have excellent mechanical strength,
Since it has gloss, transparency, moldability, moisture resistance, chemical resistance and the like, it is widely used alone or as a component of a polymer blend. However, α-olefin polymers have poor affinity for other substances due to their nonpolar molecular structure, and are inferior in various properties such as adhesion, printability, and compatibility in polymer blends.

[0003] Therefore, it has been attempted to introduce various functional groups into an α-olefin polymer. Among the functional groups, the epoxy group reacts promptly with various functional groups such as a hydroxyl group, a carboxylic acid group, an acid anhydride group, an acid halogen group, an ester group, a halogenated hydrocarbon group, a mercapto group, and an isocyanato group. It is considered to be very useful because it produces chemical bonds.

Heretofore, as a method of introducing an epoxy group into an α-olefin polymer, an unsaturated copolymer resin of propylene and a chain non-conjugated diene has been modified and an olefinic unsaturated resin in the unsaturated copolymer resin has been modified. A method of introducing an epoxy group into a saturated bond has been proposed (JP-A-61-85405). However, it is difficult to epoxidize substantially all of the unsaturated bonds by this method, so that gelation may occur at the time of molding, which tends to be restricted in use. Further, this method requires a large amount of this expensive diene to be used because the chain non-conjugated diene to be copolymerized has low copolymerizability, and the amount of the copolymer produced relative to the amount of the catalyst used (that is, Activity) also appears to be low.

On the other hand, Japanese Patent Application Laid-Open No. 1-132605 proposes an epoxidized modification of a liquid α-olefin polymer. However, the result of this proposal is:
Not only does it not have a practical mechanical strength as a molded article, but the compatibility of the polymer blend is not at a satisfactory level, and further improvement is desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve these problems by providing an epoxy group to a specific α-olefin polymer having a terminal olefinically unsaturated bond. Introducing and trying to achieve this goal.

[0007]

[Means for Solving the Problems]

[Summary of the Invention] <Summary> The epoxy group-containing α-olefin polymer according to the present invention comprises:
An olefin comprising at least one kind of α-olefin having 3 to 20 carbon atoms and having a number average molecular weight of 1,000 to 1,000,000 as measured by gel permeation chromatography, and having substantially all vinylidene bonds at one end of one side thereof Having an unsaturated bond and ¹³ C-
An unsaturated polymer in which the [mm] fraction of the triad is 0.5 or more as measured by NMR is modified, and an epoxy group is introduced into 1% or more of terminal olefinically unsaturated bonds of the polymer. It is assumed that.

<Effects> The epoxy group-containing polymer according to the present invention has various characteristic properties, for example, various kinds of inks, paints, aluminum and other metals because it contains highly reactive epoxy groups in the molecule. Adhesiveness is excellent. Further, the polymer according to the present invention exhibits an excellent compatibilizing effect even in a polymer blend with another resin.

The epoxy group-containing polymer according to the present invention has solved the problem of gelation during molding.
In addition to using no expensive special monomer such as a chain non-conjugated diene, and also having high productivity per catalyst, it is also excellent in economical efficiency.

DETAILED DESCRIPTION OF THE INVENTION <Unsaturated Polymer to be Modified><GeneralDescription> The unsaturated polymer used in the present invention has 3 to 20 carbon atoms.
Preferably, it is composed of at least one of 3 to 12 α-olefins, has an olefinically unsaturated bond at its terminal, and has a triad [mm] measured by ¹³ C-NMR.
Those having a fraction of 0.5 or more, preferably 0.6 or more, more preferably 0.75 or more are used. One end of these polymers is substantially all vinylidene bonded.

Here, the [mm] fraction of the triad is α
-Three stereoisomeric structures that a monomer unit in the olefin polymer can take as a "triad", which is the minimum unit of the stereostructure, that is, a "trimer unit", that is, (m
m] (isotactic), [mr] (heterotactic) and [rr] (syndiotactic) x
[Mm] Ratio of the number y of triads having a structure (y /
x).

Although the molecular weight of the unsaturated polymer is arbitrary, it is generally from 1,000 to 100,000 as a number average molecular weight measured by gel permeation chromatography.
0, preferably 2,000 to 500,000, and more preferably 5,000 to 200,000.

Incidentally, the measurement of ¹³ C-NMR was carried out according to JEOL. Using FX-200, measurement temperature 130 ° C., measurement frequency 50.1 MHz, spectrum width 8000 Hz, pulse repetition time 2.0 seconds, pulse width 7 μs, integration number 1
This was performed under the conditions of 0000 to 50,000 times.
The analysis of the spectrum was performed by Macromolecul of A. Zambelli.
es 21 617 (1988) and Tetsuro Asakura's Proceedings of the Society of Polymer Science, Japan 36
(8) Performed based on 2408 (1987).

Such an unsaturated polymer is contacted with a catalyst comprising a specific component (A) and component (B) or a component (C) and component (B) and an α-olefin, as described later. And can be produced by polymerization.

<Α-olefin> Examples of the α-olefin used in the present invention include propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl -1-pentene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-
Methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexane, -Vinyl bicyclo [2,2,1]
-Heptane and the like. Preferred examples of these include propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene, And particularly, propylene, 1
-Butene, 3-methyl-1-butene, and 4-methyl-1-pentene are preferred. One of these α-olefins may be used, or two or more of them may be used. In the case of a copolymer, ethylene can be used as a comonomer. When two or more α-olefins are used, the α-olefins may be randomly distributed in the unsaturated polymer or may be distributed in a block form.

<Catalyst> The unsaturated polymer used in the present invention comprises a catalyst comprising component (A) and component (B) or a catalyst comprising component (C) and component (B), and the above α -It can be produced by contacting with olefin and polymerizing.
Here, “consisting of” does not mean that the components are only those listed (ie, (A) and (B), or (C) and (B)), but rather that It does not exclude the coexistence of other components as desired.

Component (A) Component (A) is a component of the Periodic Table IVB which is π-bonded to a conjugated five-membered ring.
Group III transition metal compounds.

Among such compounds, those preferred as component (A) are those in which two conjugated five-membered rings are π-bonded to a transition metal atom of Group IVB of the Periodic Table, and It is one whose valence is filled with hydrogen, halogen (for example, Cl), or hydrocarbon residue (for example, lower alkyl group (particularly, CH ₃ ) or phenyl group).

In the conjugated five-membered ring, one or more hydrogen atoms may be substituted by a C _{1 to} C ₁₀ hydrocarbon residue. One group of such hydrocarbon residues is a lower alkyl group, and another group replaces two hydrogens of the conjugated five-membered ring and the two substituents are bonded at their ends. It has a condensed ring with a conjugated five-membered ring (for example, an indenyl group).

Specific examples of the component (A) include (a) titanocene compounds such as (i) bis (cyclopentadienyl) titanium dichloride, (ii) bis (cyclopentadienyl) titanium dimethyl, and (iii) bis (Cyclopentadienyl) titanium diphenyl, (iv) bis (ethylcyclopentadienyl) titanium dichloride,
(v) bis (butylcyclopentadienyl) titanium dichloride, (vi) bis (indenyl) titanium dichloride, (vii) bis (4,5,6,7-tetrahydro-
1-indenyl) titanium dichloride, (viii) isopropylbis (indenyl) titanium dichloride,
(ix) dimethylsilylbis (indenyl) titanium dichloride, (x) dimethylsilylbis (4,5,6,7-
Tetrahydroindenyl) titanium dichloride, etc.
(B) Zirconocene compounds such as (i) ethylenebis (indenyl) zirconium dichloride, (ii) ethylenebis (indenyl) zirconium dimethyl, (iii) ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium Dichloride, (iv) ethylene bis (4-methyl-1-indenyl) zirconium dichloride, (v) ethylene bis (4,7-dimethylindenyl) zirconium dichloride, (vi) dimethylsilylbis (indenyl) zirconium dichloride, (vii ) Dimethylsilyl (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, (viii) dimethylsilyl (2
4,5-trimethylcyclopentadienyl) (2 ′,
3 ', 5'-trimethylcyclopentadienyl) zirconium dichloride, (ix) dimethylsilylbis (4,
(C) hafnocene compounds such as 5,6,7-tetrahydroindenyl) zirconium dichloride, (i) ethylenebis (indenyl) hafnium dichloride, (ii) ethylenebis (indenyl) hafnium dimethyl, (iii) ethylenebis (4) , 5,6,7-tetrahydroindenyl) hafnium dichloride, (iv) isopropylbis (indenyl) hafnium dichloride, (v) dimethylsilyl (2,4-dimethylcyclopentadienyl) (3 ',
5'-dimethylcyclopentadienyl) hafnium dichloride, (vi) dimethylsilyl (2,4,5-trimethylcyclopentadienyl) (2 ', 3', 5'-trimethylcyclopentadienyl) hafnium dichloride,
(vii) dimethylsilylbis (indenyl) hafnium dichloride, (viii) dimethylsilylbis (4,5,6
(D) and others, such as 7-tetrahydroindenyl) hafnium dichloride.

[0021] The alumoxane used as component (B) Component (B) can be a known. Among these, the general formula

[0022]

Embedded image A cyclic alumoxane represented by

[0023]

Embedded image

The linear alumoxane represented by the formula or a mixture thereof is preferred. Where R ¹ , R ² , R
³ and R ⁴ each independently represent a hydrocarbon residue having 1 to 8 carbon atoms, preferably a hydrocarbon residue having 1 to ⁴ carbon atoms, most preferably a methyl group, and m and n each represent a number of 2 to 100. Is shown.

The above-mentioned alumoxane is produced by various known methods. Specifically, the following method can be exemplified. (A) A method in which a trialkylaluminum is directly reacted with water using an appropriate organic solvent such as toluene, benzene, or ether. (B) A method of reacting a trialkylaluminum with a salt hydrate having water of crystallization, for example, a hydrate of copper sulfate or aluminum sulfate. (C) A method of reacting trialkylaluminum with water impregnated in silica gel or the like.

Component (C) Component (C) of the catalyst of the present invention is a solid catalyst component obtained by contacting the following components (i) to (iii). Here, “obtained by contact” does not mean that the object is only an example (that is, (i) to (iii)), and that the coexistence of other components that is suitable for the purpose is not considered. Do not eliminate.

Component (i) Component (i) is a solid component for a Ziegler-type catalyst containing titanium, magnesium and halogen as essential components. Here, "contain as an essential component" means
In addition to the three components of the indications, it may contain other suitable elements, each of these elements may exist as any suitable compound, and these elements are mutually bonded It may indicate that it may be present as a result. The solid components themselves containing titanium, magnesium and halogen are known. For example, JP-A-53-45688, JP-A-54-3894, and JP-A-54-3894.
Nos. 31092, 54-39483, 54-945
No. 91, No. 54-118484, No. 54-13158
No. 9, No. 55-75411, No. 55-90510,
No. 55-90511, No. 55-127405, No. 5
5-147507, 55-155003, 56
-18609, 56-70005, 56-72
No. 001, No. 56-86905, No. 56-90807
Nos. 56-155206, 57-3803, 57-34103, 57-92007, 57-
No. 121003, No. 58-5309, No. 58-531
No. 0, No. 58-5311, No. 58-8706, No. 5
8-27732, 58-32604, 58-3
No. 2605, No. 58-67703, No. 58-1172
No. 06, No. 58-127708, No. 58-18370
No. 8, No. 58-183709, No. 59-149905
And those described in JP-A-59-149906.

The magnesium compound used as a magnesium source in the present invention includes magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate and the like. can give. Of these, preferred are magnesium halide, dialkoxymagnesium, and alkoxymagnesium halide.

The titanium compound serving as a titanium source has a general formula Ti (OR ⁵ ) _4-p X _p (where R ⁵ is a hydrocarbon residue, and preferably has about 1 to 10 carbon atoms). , X represents a halogen, and p represents a number satisfying 0 ≦ p ≦ 4.). As a specific example, TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) Cl
₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ )
₃ Cl, Ti (O-iC ₃ H ₇ ) Cl ₃ , Ti (On
_{C 4 H 9) Cl 3,} Ti (O-nC 4 H 9) 2 Cl 2,
Ti (OC ₂ H ₅ ) Br ₃ , Ti (OC ₂ H ₅ ) (OC
_{4 H 9) 2 Cl, Ti} (O-nC 4 H 9) 3 Cl, Ti
_{(O-C 6 H 5)} Cl 3, Ti (O-iC 4 H 9) 2 C
l ₂ , Ti (OC ₅ H ₁₁ ) Cl ₃ , Ti (OC ₆ H ₁₃ )
Cl ₃ , Ti (OC ₂ H ₅ ) ₄ , Ti (O-nC
_{3 H 7) 4, Ti (} O-nC 4 H 9) 4, Ti (O-i
_{C 4 H 9) 4, Ti} (O-nC 6 H 13) 4, Ti (O-
nC ₈ H ₁₇ ) ₄ , Ti [OCH ₂ CH (C ₂ H ₅ ) C ₄
H ₉ ] _{4 and the} like.

Further, a molecular compound obtained by reacting an electron donor described later with TiX ′ ₄ (here, X ′ represents a halogen) can also be used. As a specific example, TiCl ₄
CH ₃ COC ₂ H ₅ , TiCl ₄ CH ₃ CO ₂ C ₂
H ₅ , TiCl ₄ .C ₆ H ₅ NO ₂ , TiCl ₄ .CH
₃ COCl, TiCl ₄ .C ₆ H ₅ COCl, TiCl
_{4 · C 6 H 5 CO 2} C 2 H 5, TiCl 4 · ClCOC
_{2 H 5, TiCl 4 · C} 4 H 4 O and the like.

Of these titanium compounds, preferred are TiCl ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₄ H ₉ ) C
l is _3, and the like. The halogen source is usually supplied from the above-mentioned halogen compound of magnesium and / or titanium, but is supplied from a known halogenating agent such as a halide of aluminum, a halide of silicon, and a halide of phosphorus. You can also.

The halogen contained in the catalyst component is fluorine,
It may be chlorine, bromine, iodine or mixtures thereof, with chlorine being particularly preferred.

The solid components used in the present invention include, in addition to the above essential components, silicon compounds such as SiCl ₄ and CH ₃ SiCl ₃ , polymer silicon compounds such as methyl hydrogen polysiloxane, Al (OiC ₃ H ₇ ) ₃ , AlCl ₃ ,
AlBr ₃ , Al (OC ₂ H ₅ ) ₃ , Al (OCH ₃ )
Aluminum compound such as ₂ Cl and B (OC
Other components such as boron compounds such as H ₃ ) ₃ , B (OC ₂ H ₅ ) ₃ and B (OC ₆ H ₅ ) ₃ can be used, and these are solid components such as silicon, aluminum and boron. It can be left inside.

Further, when producing this solid component, it can be produced using an electron donor as an internal donor.

Electron donors (internal donors) that can be used in the production of the solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, and acid amides. Kind,
Examples thereof include oxygen-containing electron donors such as acid anhydrides, and nitrogen-containing electron donors such as ammonia, amine, nitrile, and isocyanate.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol,
Octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol,
C1-C18 alcohols such as isopropylbenzyl alcohol, (b) phenol, cresol,
C6-C2 which may have an alkyl group such as xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol, and naphthol;
Phenols having 5 to 15 carbon atoms, (c) ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone;
C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde;
(E) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, Methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, toluyl Methyl acrylate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate,
γ-butyrolactone, α-valerolactone, coumarin,
C2-C20 organic acid esters such as phthalide and ethylene carbonate, (f) ethyl silicate, butyl silicate,
Inorganic acid esters such as silicate esters such as phenyltriethoxysilane; and C 2 to C 15 acid halides such as (g) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, and phthaloyl isochloride. , Methyl ether,
Ethers having 2 to 20 carbon atoms such as ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, acid amides such as (li) acetic acid amide, benzoic acid amide, toluic acid amide, and (nu) methyl Examples thereof include amines such as amine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine; and nitriles such as (ル) acetonitrile, benzonitrile, and tolunitrile. Two or more of these electron donors can be used. Of these, preferred are organic acid esters and organic acid halides, and particularly preferred are cellosolve acetate, phthalate esters and phthalic halides.

The amount of each of the above components can be arbitrary as long as the effects of the present invention are recognized.
The following range is preferred.

The titanium compound is used in a molar ratio of 1 × 10 ^-4 to 1 with respect to the magnesium compound used.
000, preferably 0.01 to 10. When a compound for that purpose is used as a halogen source, the amount used is 1 × 10 5 in molar ratio with respect to the amount of magnesium used irrespective of whether the titanium compound and / or the magnesium compound contains halogen or not. ^{-2 to} 1000, preferably 0.1 to 10
0.

The amount of the silicon, aluminum and boron compounds to be used is 1 × 10 ^{−3 to} 100, preferably 0.01 to 0.01 in terms of a molar ratio with respect to the above-mentioned magnesium compound.
1, within the range.

The amount of the electron donating compound to be used is 1 × 10 ⁻³ to 1: 1 in molar ratio with respect to the amount of the above magnesium compound to be used.
10, preferably in the range of 0.01 to 5.

The solid component for producing the component (i) is prepared by using the above-mentioned titanium source, magnesium source and halogen source, and if necessary, other components such as an electron donor, for example, by the following production method. Manufactured. (A) A method in which a magnesium halide is brought into contact with an electron donor, if necessary, and a titanium-containing compound. (B) A method in which alumina or magnesia is treated with a phosphorus halide compound, and a magnesium halide, an electron donor, and a titanium halide-containing compound are brought into contact therewith. (C) A method of contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound.

As the polymer silicon compound, a compound represented by the following formula is suitable.

[0043]

Embedded image

(Where R ⁶ is a hydrocarbon residue having about 1 to 10 carbon atoms, and q is 1)
こ れ ら 100 centistokes). Of these, methyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentane Methylcyclopentasiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane and the like are preferable. (D) A method in which a magnesium compound is dissolved in a titanium tetraalkoxide and an electron donor, and the solid component precipitated with a halogenating agent or a titanium halide compound is brought into contact with the titanium compound. (E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to react with a halogenating agent, a reducing agent, and the like, and then contacted with an electron donor and a titanium compound as necessary. (F) A method of contacting an alkoxymagnesium compound with a halogenating agent and / or a titanium compound in the presence or absence of an electron donor.

Component (ii) Component (ii) used to produce component (C) has the general formula R ⁷ _r X _s Si (OR ⁸ ) _4-rs (where R ⁷ and R ⁸ are hydrocarbons) X is halogen, r
And s are 0 ≦ r ≦ 3 and 0 ≦ s ≦ 3, respectively, and 0 ≦ r + s ≦ 3. R ⁷ and R ⁸ are each preferably about 1 to 20, preferably 1 to 10, hydrocarbon residues. X is preferably chlorine at least from the viewpoint of economy.

As a specific example, (CH ₃ ) Si (OCH
₃ ) ₃ , (CH ₃ ) Si (OC ₂ H ₅ ) ₃ , (C
_{2 H 5) 2 Si (OCH} 3) 2, (n-C 6 H 11) Si
(OCH ₃ ) ₃ , (C ₂ H ₅ ) Si (OC ₂ H ₅ ) ₃ ,
_{(N-C 10 H 21)} Si (OC 2 H 5) 3, (CH 2 = C
H) Si (OCH ₃ ) ₃ , Cl (CH ₂ ) ₃ Si (OC
H ₃ ) ₃ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₃
Cl, (C ₂ H ₅ ) ₂ Si (OC ₂ H ₅ ) ₂ , (C ₁₇ H
₃₅ ) Si (OCH ₃ ) ₃ , Si (OC ₂ H ₅ ) ₄ , (C
_{6 H 5) Si (OCH 3} ) 3, Si (OCH 3) 2 Cl
₂ , (C ₆ H ₅ ) ₂ Si (OCH ₃ ) ₂ , (C ₆ H ₅ )
(CH ₃ ) Si (OCH ₃ ) ₂ , (C ₆ H ₅ ) Si (O
C ₂ H ₅ ) ₃ , (C ₆ H ₅ ) ₂ Si (OC ₂ H ₅ ) ₂ ,
NC (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , (C ₆ H ₅ )
_{(CH 3) Si (OC 2} H 5) 2, (n-C 3 H 7) S
i (OC ₂ H ₅ ) ₃ , (CH ₃ ) Si (OC
_{3 H 7) 3, (C} 6 H 5) (CH 2) Si (OC
₂ H _{5) 3,}

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

(CH ₃ ) ₃ CSi (CH ₃ ) (OC
H ₃ ) ₂ , (CH ₃ ) ₃ CSi (HC (CH ₃ ) ₂ )
(OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC
_{2 H 5) 2, (C} 2 H 5) 3 CSi (CH 3) (OCH
₃ ) ₂ , (CH ₃ ) (C ₂ H ₅ ) CH-Si (CH ₃ )
(OCH ₃ ) ₂ , ((CH ₃ ) ₂ CHCH ₂ ) Si (O
CH ₃ ) ₂ , C ₂ H ₅ C (CH ₃ ) ₂ Si (CH ₃ )
(OCH ₃ ) ₂ , C ₂ H ₅ C (CH ₃ ) ₂ Si (C
H ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (OCH
₃ ) ₃ , (CH ₃ ) ₃ CSi (OC ₂ H ₅ ) ₃ , (C ₂
H ₅ ) ₃ CSi (OC ₂ H ₅ ) ₃ , (CH ₃ ) (C ₂ H
₅ ) CHSi (OCH ₃ ) _{3 and the} like. Of these, preferred are those in which the carbon at the α-position of R ⁷ is secondary or tertiary and a branched chain hydrocarbon residue having 3 to 20 carbon atoms, particularly the carbon at the α-position of R ⁷ is tertiary. It is a silicon compound having a branched chain hydrocarbon residue having 4 to 10 carbon atoms.

Component (iii) Component (ii) to constitute a solid catalyst component for a Ziegler-type catalyst
i) is an organometallic compound of a metal of Groups I to III of the periodic table.

As an organometallic compound, this compound has at least one organic group-metal bond. In this case, the organic group has about 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
To a degree, hydrocarbyl groups are representative.

The metal in this compound is lithium,
Magnesium, aluminum and zinc, especially aluminum, are typical. The remaining valence (if any) of the metal of the organometallic compound in which at least one of the valences is filled with an organic group is a hydrogen atom, a halogen atom,
A hydrocarbyloxy group (the hydrocarbyl group has about 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms) or the metal via an oxygen atom (specifically, -O-Al (CH _{3 in} the case of methylalumoxane) )-), Others are satisfied.

Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium and tertiarybutyllithium, (b) butylethylmagnesium, dibutylmagnesium and hexylethylmagnesium. , Butylmagnesium chloride,
Organomagnesium compounds such as tert-butylmagnesium bromide; (c) organozinc compounds such as diethylzinc and dibutylzinc; (d) trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-
Hexylaluminum, diethylaluminum chloride, diethylaluminum hydride, diethylaluminum ethoxide, ethylaluminum sesquichloride,
Organic aluminum compounds such as ethylaluminum dichloride and methylaluminoxane can be mentioned. Of these, organoaluminum compounds are particularly preferred.

Preparation of the solid catalyst component (C) The contacting method and the amount of the components (i) to (iii) can be any as long as the effects of the present invention are recognized. Conditions are preferred.

The quantitative ratio of component (i) to component (ii) is 0.01 to 1000, preferably 0.01 to 1000, in terms of the atomic ratio of silicon of component (ii) to the titanium component constituting component (i). 0.1 to 100. Component (i) of component (iii)
Is the metal atom ratio of the organometallic compound (metal /
0.01-100, preferably 0.1-3
0.

The order of contact and the number of times of contact of the components (i) to (iii) are not particularly limited. For example, the following methods can be mentioned. (B) Component (i) → Component (ii) → Component (iii) (b) Component (i) → Component (iii) → Component (ii) (c) Component (i) → Component (ii) + Component ( iii)｝ → ｛component
(ii) + component (iii)｝ (d) ｛component (ii) + component (iii)｝ → component (i) (e) Method of contacting components (i), (ii) and (iii) simultaneously (f In the methods (a) to (d), a cleaning step is performed between each step.

The contact temperature is about -50 to 200 ° C, preferably about 0 to 100 ° C. As a contact method,
Examples thereof include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring / pulverizing machine, and a method of bringing into contact by stirring in the presence of an inert diluent. Inert diluents used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes and the like.

Optional Components In contacting these components, other components other than components (i) to (iii), such as methyl hydrogen polysiloxane, ethyl borate, aluminum triisopropoxy, etc., may be used as long as the effects of the present invention are not impaired. , Aluminum trichloride, silicon tetrachloride, general formula Ti (OR ⁹ ) _4-t X
It is also possible to add a titanium compound represented by _t (where 0 ≦ t ≦ 4, R ⁹ represents a hydrocarbon residue and X represents a halogen), a trivalent titanium compound, tungsten hexachloride, molybdenum pentachloride and the like. It is.

<Production of Unsaturated Polymer> As a method for polymerizing an α-olefin using a catalyst comprising the catalyst component (A) and the component (B), it is a matter of course that ordinary slurry polymerization can be employed. A liquid phase solventless polymerization method using substantially no solvent, a solution polymerization method, or a gas phase polymerization method can be employed. Further, the polymerization can be carried out by a method of performing continuous polymerization, batch polymerization or preliminary polymerization. As a polymerization solvent in the case of slurry polymerization, hexane, heptane, pentane, cyclohexane, benzene,
A single or mixture of a saturated aliphatic or aromatic hydrocarbon such as toluene is used. The polymerization temperature is from -78 ° C to 2
The temperature is about 00 ° C., preferably 0 ° C. to 150 ° C. At this time, hydrogen can be used as a molecular weight regulator in an auxiliary manner.

The amounts of component (A) and component (B) used are as follows:
The atomic ratio of the aluminum atom in the component (B) to the transition metal in the component (A) is from 0.01 to 100,000, preferably from 0.1 to 3
0000. The component (A) and the component (B) can be brought into contact separately during the polymerization, or they can be brought into contact outside the polymerization tank in advance.

The catalyst comprising the component (C) and the component (B) can be prepared by mixing the two components and, if necessary, the third component in a polymerization tank or in the coexistence of an olefin to be polymerized, or outside the polymerization tank. It can be formed by contacting several times at a time, stepwise or in the presence of the olefin to be polymerized.

Component (B) is used in a molar ratio (Al / Ti) of 0.1 to the titanium component constituting component (C).
１０００1000, preferably 1-100. There is no particular limitation on the method of supplying the components (C) and (B) to the contact site, but they are each dispersed in an aliphatic hydrocarbon solvent such as hexane or heptane, and separately added to the polymerization vessel or contacted in advance. Usually, it is added to the polymerization tank. The component (C) and the component (B) in a solid state may be separately added to the polymerization tank.

In the olefin polymerization method, the catalyst described above is used
It consists of contacting an olefin at a temperature of 150 ° C. or higher to carry out polymerization.

The upper limit of the polymerization temperature is about 300 ° C.
A particularly preferred polymerization temperature is 150 to 250 ° C.

The polymerization of the olefin can be carried out according to a liquid phase solventless polymerization, a solution polymerization or a gas phase polymerization method using substantially no solvent. When the polymerization solvent is used, an inert solvent such as hexane, heptane, cyclohexane, toluene, octane, decane, paraffin, and white kerosene can be used.

The polymerization pressure is not particularly limited.
It is about 1000 kg / cm ² G. The polymerization can be carried out by any of continuous polymerization and batch polymerization.

<Modification of Unsaturated Polymer> In the present invention, the above unsaturated polymer is modified to introduce an epoxy group into the terminal olefinically unsaturated bond.

In the present invention, the introduction of an epoxy group into an olefinically unsaturated bond means that an epoxy group is derived using the olefinically unsaturated bond, and oxygen is bonded to the olefinically unsaturated bond. Then, an epoxy group can be introduced by a method such as conversion to an epoxy group or binding of an epoxy group-containing compound to an olefinically unsaturated bond.

The amount of the epoxy group introduced is at least 1%, preferably at least 3%, more preferably at least 5%, most preferably at least 10% of the olefinically unsaturated bond in the unsaturated polymer.
That is all. When the introduction amount is less than 1%, the content of the epoxy group is low and the modification effect is poor.

The method for introducing an epoxy group into the olefinically unsaturated bond at the terminal of the unsaturated polymer is not particularly limited.
Oxidation of olefinic unsaturated bond by oxidation
It is roughly classified into a method by an addition reaction of a compound containing one or more epoxy groups to an olefinically unsaturated bond, and others.

Examples of the method of oxidizing the olefinic unsaturated bond include (a) oxidation with a peracid such as formic acid, peracetic acid, and perbenzoic acid, and (b) in the presence of a metal porphyrin complex such as a manganese porphyrin complex. Or oxidation with sodium hypochlorite or the like in the absence, (c) oxidation with hydrogen peroxide, hydroperoxide, or the like in the presence or absence of a catalyst such as vanadium, tungsten, or molybdenum compound; ) Oxidation with alkaline hydrogen peroxide,
(E) Neutralization of the adduct with an alkali in an acetic acid / t-butyl hypochlorite system.

On the other hand, a group of compounds containing one or more epoxy groups in the molecule are those having active hydrogen to be subjected to an addition reaction to an olefinically unsaturated bond, in particular, a Michael type addition reaction. Examples thereof include thiol compounds such as thioglycidol and glycidyl thioglycolate.

The reaction is carried out in a state in which the polymer is swollen or dissolved by a solvent, or in a molten state. Reactions in the dissolved or molten state are preferred. The solvent to be used should be appropriately selected depending on the type of the reaction, but may include aliphatic, alicyclic, and aromatic hydrocarbons and their halides, esters, ketones, ethers having 6 or more carbon atoms, and carbon disulfide. In many cases, and can be used as a mixture of two or more solvents. The selectivity of the reaction is not necessarily required to be 100%, and a product by a side reaction may be mixed if an epoxy group is substantially introduced.

<Modified Polymer> The modified polymer according to the present invention has a characteristic property due to having an epoxy group at a terminal. For example, various printing inks,
Excellent paint adhesion and imparts dyeability. Excellent adhesion to copper and other metals and excellent adhesion to other resins. Because of its excellent adhesion to other resins, it is advantageous to use this as a binder between incompatible resins, especially at the interface between a polyolefin-based resin and a resin having a functional group reactive with an epoxy group. Contributes to improvement in strength. In addition, utilizing the reactivity of the epoxy group, for example, antioxidant, ultraviolet absorption, antifogging, photosensitive, fluorescent, color,
The above properties can be imparted by introducing a compound having a functional group such as chelating ability. In addition to the above, the modified polymer according to the present invention has excellent mechanical strength.

[0077]

EXAMPLES <Production Example 1 of Unsaturated Polymer> Production of Catalyst Component (A) Ethylenebis (indenyl) zirconium dichloride (A-1) and dimethylsilylbis (indenyl) dichloride (A-2) were prepared by the method described in "J. .Orgmet.Chem. '' (342) 21
-29 1988 and J. Orgmet.Chem. (369) 359-370 19
Synthesized according to 89 .

Preparation of Catalyst Component (B) 50 g of copper sulfate pentahydrate was added to 565 ml of a toluene solution containing 48.2 g of trimethylaluminum at 0 ° C. with stirring.
Feed every 5 minutes at g intervals. After completion, the solution was slowly heated to 25 ° C., reacted at 25 ° C. for 2 hours, and further cooled to 35 ° C.
The temperature was raised to ° C. and the reaction was carried out for 2 days. The remaining copper sulfate solid is separated to obtain a toluene solution of alumoxane. The concentration of methylalumoxane is 27.3 mg / ml (2.7 w / v%)
Met.

Preparation of Resin-A In a 1.0-liter stainless steel autoclave equipped with a stirring and temperature control device, 400 ml of sufficiently dehydrated and deoxygenated toluene, 580 mg of methylalumoxane and the component (A- 1) to 0.418
Milligram (0.001 mmol) was introduced, and polymerization was carried out at 40 ° C. for 4 hours at a propylene pressure of 7 kg / cm ² G. After the completion of the polymerization, the polymerization solution was extracted into 3 liters of methanol, and the polymer was separated by filtration and dried, whereby 180 g of a resin (Resin-A) was recovered. As a result of measurement by gel permeation chromatography, the product was found to have a number average molecular weight (Mn) of 18.7 × 10 ³ and a molecular weight distribution (MW / Mn).
1.99. JEOL. As a result of ¹³ C-NMR measurement by FX-200, the [mm] fraction of the triad was 0.888, and one end was a vinylidene bond (0.79 per 1000 carbon atoms).

Preparation of Resin-B 400 ml of toluene sufficiently dehydrated and deoxygenated in a 1.0 liter stainless steel autoclave equipped with a stirring and temperature control device, 20 ml of 1-hexene, 239 mg of methylalumoxane and 0.62 mg (1.37 × 10 ⁻⁶ mol) of (A-2) was introduced as the component (A), and the propylene pressure was 3 kg.
/ Cm ² G at 15 ° C. for 4 hours. After the completion of the polymerization, the polymerization reaction solution was extracted into 3 liters of ethanol, filtered and dried to obtain 22.4 g of a resin (Resin-B). As a result of ¹³ C-NMR measurement, the content of 1-hexene was 0.9 mol%, and one of the terminals was a vinylidene bond (0.32 per 1000 carbon atoms).
), And the [mm] fraction of the triad showed a value of 0.94. The number average molecular weight (Mn) was 43.6 × 10 ³ , and the molecular weight distribution (MW / Mn) was 2.23.

Polymerization was carried out under the same conditions as for resin A except that bis (cyclopentadienyl) zirconium dichloride was used as component (A) for producing resin C. After completion of the polymerization, the polymerization solution was withdrawn, 200 ml of ethanol and 500 ml of water were added, and the upper organic layer was recovered. Then, toluene was removed by an evaporator to obtain a liquid resin (resin-C) 15.
3 grams were collected. The triad [mm] fraction was 0.302, the number average molecular weight (Mn) was 1340, the molecular weight distribution (MW / Mn) was 2.01, and all of the one ends were vinylidene bonds (11.6 carbon atoms per 1000 carbon atoms). )Met.

Preparation of Catalyst Component (C) In a flask sufficiently purged with nitrogen, dehydrated and deoxygenated n
-200 ml of heptane are introduced and then MgC
l ₂ 0.4 _{moles, Ti (O-nC 4 H} 9) 4 0.8
Mole was introduced and reacted at 95 ° C. for 2 hours. After the reaction,
The temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane to obtain a solid component.

Then, 50 ml of n-heptane purified in the same manner as described above was introduced into a flask sufficiently purged with nitrogen, and the solid component synthesized as described above was added in an amount of 0.2 mg in terms of Mg atoms.
4 moles were introduced. Then, 0.8 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After the completion of the reaction, the resultant was washed with n-heptane.

Into a flask sufficiently purged with nitrogen, 50 ml of sufficiently purified n-heptane was introduced, then 5 g of the solid component obtained above was introduced, and then component (ii)
(CH ₃ ) ₃ CSi (CH ₃ ) as a silicon compound of
2.8 ml of (OCH ₃ ) ₂ were introduced, and 1.5 g of triethylaluminum as the component (iii) was further introduced, and the mixture was contacted at 30 ° C. for 2 hours. After the contact is completed, this is thoroughly washed with n-heptane, and the component (C)
And

Preparation of Resin-D In a 1.5 liter stainless steel autoclave with stirring and temperature control, 500 ml of sufficiently dehydrated and deoxygenated n-paraffin, 50 mg of the component (B) and the above Component (C) produced in
Was introduced at a polymerization pressure of 5 kg / cm ² G, a polymerization temperature of 170 ° C., and a polymerization time of 2 hours. After the completion of the polymerization, the obtained polymer solution was treated with ethanol, separated from the polymer and n-paraffin, and dried to obtain a polymer. As a result, 54.2
Grams of polymer were obtained. As a result of gel permeation chromatography, this polymer had a number average molecular weight (Mn) of 2.57 × 10 ⁴ and a molecular weight distribution (Mw /
Mn) was 6.876. Also, as a result of measurement of ¹³ C-NMR, the [mm] fraction of the triad was 0.953,
All one ends were vinylidene linked.

Example 1 In a dried 300 ml flask, 5 g of the resin A obtained in Production Example 1 of the unsaturated polymer was added at 100 ° C. with 100 ml of xylene.
Dissolved in. A solution prepared by dissolving 0.8 g of metachloroperbenzoic acid in 40 ml of xylene was added dropwise to this solution over 1 hour, and the reaction was carried out at 100 ° C. for 3 hours. afterwards,
The polymer solution was poured into a large amount of cold methanol to precipitate a polymer, and the polymer was separated by filtration, washed, and then dried under reduced pressure to obtain a modified polymer. It was confirmed by NMR spectroscopy that the epoxy group was introduced into the polymer, and the conversion of the terminal olefinically unsaturated bond into the epoxy group was 71%.
%.

Example 2 In a dried 300 ml flask, 5 g of the resin A obtained in Production Example 1 of the unsaturated polymer was dissolved at 100 ° C. in 100 ml of xylene. To this solution, 0.4 g of cumene hydroperoxide, 0.01 g of molybdenum octylate and 0.05 g of triisopropyl borate were added and reacted at 110 ° C. for 3 hours. Thereafter, the polymer solution was poured into a large amount of cold acetone to precipitate a polymer, and after filtering,
After washing with a 2N-NaOH aqueous solution and further washing with water, the polymer was dried under reduced pressure to obtain a modified polymer.

NMR spectroscopy confirmed that an epoxy group had been introduced into the polymer, and it was found that the conversion of terminal olefinically unsaturated bonds into epoxy groups was 67%.

Example 3 Example 1 was repeated except that the resin B obtained in the unsaturated polymer production example 1 was used instead of the resin A in the example 1.
The reaction was performed in exactly the same manner as described above. NMR spectroscopy confirmed that an epoxy group had been introduced into the polymer, and it was found that the conversion of terminal olefinically unsaturated bonds into epoxy groups was 58%.

Comparative Example 1 In a dried 300 ml flask, 5 g of the resin C obtained in Production Example 1 of the unsaturated polymer was added at 100 ° C. with 100 ml of xylene.
Dissolved in. To this solution, a solution of 2.0 g of metachloroperbenzoic acid dissolved in 80 ml of xylene was added dropwise over 1 hour, and the reaction was carried out at 100 ° C. for 3 hours. afterwards,
The polymer solution was cooled to 25 ° C. and ₃ g of Na ₂ SO 3
And stirred at 25 ° C. for 30 minutes.
After washing with an aqueous solution of O ₃ and water, xylene was distilled off and dried under reduced pressure to obtain a modified polymer. NMR spectroscopy confirmed that an epoxy group had been introduced into the polymer, and it was found that the conversion of terminal olefinically unsaturated bonds to epoxy groups was 82%.

<Example 4> A procedure was performed in exactly the same manner as in Example 1 except that resin A was changed to resin D. NMR spectroscopy confirmed that an epoxy group had been introduced into the polymer, and the conversion of the terminal olefinically unsaturated bond into an epoxy group was found to be 65%.

<Application Example-1> A polypropylene resin (MA8 manufactured by Mitsubishi Yuka Co., Ltd.) and a maleic acid-modified polyphenylene ether (maleic acid content 0.5% by weight, number average molecular weight Mn = 9200, weight average molecular weight Mw = 31000) and Example-1 and Example-3.
Alternatively, the epoxy group-containing α-olefin polymer obtained in Comparative Example 1 was melted for 6 minutes at 280 ° C. and a rotation speed of 60 rpm with a composition shown in Table 1 using a plastmill manufactured by Toyo Seiki Co., Ltd. with an internal volume of 60 ml. Kneaded. The obtained mixture is heated at 280 ° C.
Under the conditions described above to form a sheet having a thickness of 2 mm. Various test pieces were cut out from this sheet and used for physical property evaluation.

<Measurement and Evaluation Methods> (1) Flexural Modulus A test piece having a width of 25 mm and a length of 80 mm was cut and subjected to JIS.
It measured using the Instron testing machine according to K7203. (2) Izod impact strength Impact strength is JIS K711
According to 0, three test pieces having a thickness of 2 mm
The notched Izod impact strength at ℃ was measured.

<Results> Table 1 shows the results obtained by the above method. As is clear from Table 1, the composition using the epoxy group-containing α-olefin polymer according to the present invention shows high impact strength.

[0095]

[Table 1]

[0096]

According to the present invention, the epoxy group-containing polymer is
Excellent in various characteristic properties, for example, adhesion to various inks, paints or aluminum and other metals, exhibits excellent compatibilizing effect even in polymer blends with other resins, and has a problem of gelation during molding. It is not economical because the cost per catalyst is high in addition to the use of expensive special monomers such as linear non-conjugated dienes. [Means for Solving the Problem].

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshihiko Kanno 1 Tohocho, Yokkaichi-shi, Mie Pref. In the Yokkaichi Research Institute, Mitsubishi Petrochemical Co., Ltd. (56) References JP-A-49-13292 (JP, A) JP-A-61-85405 (JP, A) JP-A-63-305104 (JP, A) 1-132605 (JP, A) JP-A-4-20505 (JP, A) JP-B-48-13330 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/02 C08G 59/34 C08F 8/08

Claims (1)

(57) [Claims] 1. A gel permeation chromatograph comprising at least one α-olefin having 3 to 20 carbon atoms.
Number average molecular weight from 1000 to 1000 as measured by fee
000 polymer, with substantially all of its one end
It has an olefinically unsaturated bond consisting of a vinylidene bond , and has a triad [mm] determined by ¹³ C-NMR.
An unsaturated polymer having a fraction of 0.5 or more, wherein an epoxy group is introduced into 1% or more of terminal olefinically unsaturated bonds of the polymer, and an epoxy group-containing α-
Olefin polymer.