JPH05320256A - A method for producing .ALPHA.-olefin polymers. - Google Patents

Abstract

(57) [Summary] [Structure] An α-olefin is copolymerized with a polar vinyl monomer represented by the following formula (I) by a Ziegler type catalyst, and the polar vinyl monomer is equivalent to active hydrogen of its polar group. A complex of an organoaluminum compound represented by the following formula (II) in a mole or more, wherein the Ziegler-type catalyst is composed of a titanium trichloride compound and an organoaluminum compound. -Process for producing olefin polymers. [Chemical 1] (Here, Y is a hydrocarbon group having 3 to 20 carbon atoms, and Z is
Is _{^{-NH 2, -NHR 1, (R}} 1 is a hydrocarbon group having 1 to 20 carbon atoms.) - OH or -COOH, m
Is an integer of 1 to 3. ) AlR ² R ³ R ⁴ (II) (wherein R ² , R ³ and R ⁴ each independently represent an alkyl group or an aryl group.) [Effect] A polar vinyl monomer is contained in a high content, An α-olefin polymer having excellent adhesiveness, printability, hydrophilicity, and compatibility with polymer blends can be obtained in high yield.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

TECHNICAL FIELD The present invention relates to a process for producing a copolymer comprising a polar vinyl monomer and an olefin. More specifically, the present invention provides a high-yield copolymer having a high content of a vinyl monomer having a polar group and having excellent adhesiveness, printability, hydrophilicity, compatibility with a polymer blend, and the like. And a process for producing the copolymer.

[0002]

2. Description of the Related Art Homopolymers of α-olefins (including ethylene in the present invention) and copolymers thereof are inexpensive and have excellent mechanical strength, gloss and transparency. Since it has moldability, moisture resistance and chemical resistance, it is widely used. However, since the olefin polymer has a non-polar molecular structure, it has poor affinity with other substances, and has various properties such as adhesiveness, printability, paintability, antistatic properties, and compatibility with polymer blends. Inferior

In order to improve it, a method has been proposed in which a polar vinyl monomer is copolymerized with an olefin using a Ziegler-Natta type catalyst to give a polar group to the polyolefin. For example, JP-A-55-98209 discloses a method of using a monomer represented by the formula (III) as a polar vinyl monomer in the copolymerization of α-olefin and a polar vinyl monomer.

[0004]

[Chemical 2]

(R ⁵ is a hydrogen atom or a methyl group,
R ⁶ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z ′ is —OH or —COOH. n = 2-1
It is 6. Further, US Pat. No. 3,492,277 discloses a method in which an organoaluminum compound and a polar vinyl monomer are heated at 60 to 150 ° C. and then the product is used for polymerization.

However, even if these methods are used, the amount of the polar vinyl monomer copolymerized in the polyolefin is generally small, and the activity of the Ziegler-Natta type catalyst may be greatly deteriorated. It is hard to say that the modifying effect by the group is still at a practical level in the production of the copolymer.

[0007]

As described above, it was not easy to produce a copolymer in which a polar vinyl monomer was copolymerized at a high content, while keeping the activity of the catalyst at a sufficiently satisfactory level.

[0008]

[Summary of the Invention] <Summary> The present invention is intended to solve these problems, and the activity of the Ziegler-Natta type catalyst is sufficiently high. And a process for producing a copolymer having a high content of polar vinyl monomers.

That is, the method for producing an α-olefin polymer according to the present invention comprises copolymerizing an α-olefin with a polar vinyl monomer represented by the following formula (I) using a Ziegler type catalyst. Is a complex with an organoaluminum compound represented by the following formula (II) in an equimolar amount or more with the active hydrogen of the polar group, and the Ziegler type catalyst comprises a titanium trichloride compound and an organoaluminum compound. It is characterized by being.

[0010]

[Chemical 3]

(Here, Y is a hydrocarbon group having 3 to 20 carbon atoms, Z is -NH ₂ , -NHR ¹ (R ¹ is ¹ carbon atom.
~ 20 hydrocarbon groups. ), -OH or -COO
H and m is an integer of 1 to 3. ) AlR ² R ³ R ⁴ (II) (wherein R ² , R ³ and R ⁴ each independently represents an alkyl group or an aryl group.)

<Effect> According to the present invention, an α-olefin polymer containing a polar vinyl monomer in a high content and excellent in adhesiveness, printability, hydrophilicity and compatibility in a polymer blend can be obtained in a high yield. Obtainable.

[Detailed Description of the Invention] The method for producing the copolymer of the present invention will be described in detail.

<Α-Olefin> One of the monomer components constituting the copolymer is α-olefin (including ethylene in the present invention). In the present invention, α-olefins having about 2 to 12 carbon atoms, particularly 2 to 8 carbon atoms are preferable. Specific examples of such α-olefins include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-
Butene, 3-methyl-1-pentene, 4-methyl-1-
Pentene, 3,3-Dimethyl-1-butene, 4,4-Dimethyl-1-pentene, 3-Methyl-1-hexene, 4
Examples thereof include -methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene, allylcyclopentane, vinylcyclopropane, vinylcyclohexane and the like. Of these, the preferred one is
Ethylene, propylene, 1-butene, 1-hexene, 3
-Methyl-1-butene, 3-methyl-1-pentene, 4
-Methyl-1-pentene, 5-methyl-1-hexene and the like, particularly ethylene, propylene, 1-butene,
3-Methyl-1-butene or 4-methyl-1-pentene are preferred. These α-olefins may be used alone or in combination of two or more.

<Polar Vinyl Monomer> Another monomer component which constitutes the copolymer of the present invention together with the above-mentioned α-olefin is a polar vinyl monomer. In the present invention, those represented by the formula (I) can be used.

[0016]

[Chemical 4]

(Here, Y is a hydrocarbon group having 3 to 20 carbon atoms, Z is -NH ₂ , -NHR ¹ (R ¹ is ¹ carbon atom.
~ 20 hydrocarbon groups. ), -OH or -COO
H and m is an integer of 1 to 3. )

In the present invention, among the compounds of formula (I), Y
Is preferably a hydrocarbon group having 4 or more carbon atoms, particularly 7 or more carbon atoms. Specific examples of the polar vinyl monomer represented by the formula (I) include 5-hexenoic acid, 6-heptenoic acid,
7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-
Undecenoic acid, 1-hydroxy-4-pentene, 1-hydroxy-5-hexene, 1-hydroxy-6-heptene, 1-hydroxy-7-octene, 1-hydroxy-
8-nonene, 1-hydroxy-9-decene, 1-hydroxy-10-undecene, 1-amino-6-heptene,
1-amino-7-octene, 1-amino-8-nonene,
1-amino-9-decene, 1-amino-10-undecene, 1- (N-methylamino) -10-undecene, 1
-(N-Ethylamino) -10-undecene and 1-
(N-phenylamino) -10-undecene and the like can be mentioned. These polar vinyl monomers can be used alone or in combination of two or more kinds.

<Organoaluminum Compound> An organoaluminum compound which is complexed with the above polar vinyl monomer to form a complex compound with the vinyl monomer is represented by the following formula (II). AlR ² R ³ R ⁴ (II) (R ² , R ³ and R ⁴ are each independently an alkyl group or an aryl group.)

The alkyl group represented by R ^{2 to} R ⁴ is preferably one having about 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms. R ² , R ³ and R ⁴ are the same,
May be different. Specific examples of such compounds include:
Al (CH ₃ ) ₃ , Al (C ₂ H ₅ ) ₃ , Al (iC _{3
H 7) 3, Al (nC} 3 H 7) 3, Al (iC 4 H 9)
₃ , Al (nC ₄ H ₉ ) ₃ , Al (iC ₅ H ₁₁ ) ₃ , A
l (nC ₅ H ₁₁ ) ₃ , Al (iC ₆ H ₁₃ ) ₃ , Al (n
_{C 6 H 13) 3, Al} (iC 7 H 15) 3, Al (nC 7 H
₁₅ ) ₃ , Al (iC ₈ H ₁₇ ), Al (nC ₈ H ₁₇ ), Al (C ₁₀ H ₂₁ ) _{3 and the} like. Among these organoaluminum compounds, preferred is Al (C ₂ H
₅ ) ₃ , Al (iC ₃ H ₇ ) ₃ , Al (nC
₃ H ₇ ) ₃ , Al (iC ₄ H ₉ ) ₃ , Al (nC
₄ H ₉ ) ₃ , Al (iC ₅ H ₁₁ ) ₃ , Al (nC
₅ H ₁₁ ) ₃ , Al (iC ₆ H ₁₃ ) ₃ , Al (nC
₆ H ₁₃ ) ₃ , and more preferred is Al (iC _{3).
H 7) 3, Al (nC} 3 H 7) 3, Al (iC 4 H 9)
₃ , Al (nC ₄ H ₉ ) ₃ , Al (iC ₅ H ₁₁ ) ₃ , A
1 (nC ₅ H ₁₁ ) ₃ and most preferred is Al
(IC ₄ H ₉ ). These organoaluminum compounds can be used alone or in combination of two or more.

<Synthesis of Complex Compound> The above-mentioned polar vinyl monomer and the organoaluminum compound of the formula (II) are synthesized in the presence of the above-mentioned polar vinyl monomer and the organoaluminum compound, if necessary, in the presence of a solvent. It can be performed by contacting with.

In this case, the contact amount of the organoaluminum compound of the formula (II) needs to be at least equimolar to the active hydrogen of the polar group of the polar vinyl monomer, that is, at a molar ratio of 1 or more. If this condition is not satisfied, the activity of the Ziegler type catalyst used for the copolymerization will decrease.

Here, the term "organoaluminum compound having an equimolar amount or more with respect to the active hydrogen of the polar group of the polar vinyl monomer" means, for example, 1 mol of the polar vinyl monomer having one -OH group having one active hydrogen in the molecule. In contrast, the organoaluminum compound has 1 mol or more and two active hydrogens-
The organoaluminum compound means 2 moles or more with respect to 1 mole of the polar vinyl monomer having one NH ₂ group in the molecule.

The contact temperature is usually about 0 to 200 ° C., preferably 0 to 150 ° C. Further, the contact substance can be heated at the time of contact.

The solvent used has 5 to 18 carbon atoms.
Suitable are aliphatic, cycloaliphatic and aromatic hydrocarbons, and chlorinated hydrocarbons. Depending on the solubility of the complex compound, it is also possible to use them by appropriately mixing them. For example, in the present invention, various solvents such as pentane, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, benzyl chloride, monochlorobenzene and dichloroethane can be preferably used.

<Production of α-Olefin Polymer> (Catalyst) The method for producing an α-olefin polymer according to the present invention comprises the steps of adding the α-olefin and the complex compound of the polar monomer to a titanium trichloride compound and an organic compound. The polymerization is carried out by contacting with a Ziegler type catalyst composed of an aluminum compound. Here, "composed of a titanium trichloride compound and an organoaluminum compound" means that a third component other than the titanium trichloride compound and the organoaluminum compound can be used as long as the effects of the present invention are not impaired. Means there is. A typical example of such a third component is a component for increasing the activity of the catalyst or the crystallinity of the resulting copolymer, for example, an ester such as ethylbenzoate, n-
There are ethers such as butyl ether and organic phosphorus compounds such as triphenyl phosphite.

As the titanium trichloride catalyst component to be used, a carrier composed mainly of various α, β, γ and δ type titanium trichloride compounds and magnesium chloride compounds, on which these titanium trichloride compounds are supported, Is typical.
In particular, a tri-aluminum chloride is extracted and removed from a eutectic mixture of titanium trichloride and aluminum chloride obtained by reducing titanium tetrachloride with an organoaluminum compound, using a complexing agent (for example, isoamyl ether). A titanium chloride composition (which is activated with a dialkylaluminum halide or the like when used) is preferable (see, for example, JP-A-47-34478).

In the present invention, the organoaluminum compound as a cocatalyst used in combination with the above-mentioned titanium trichloride catalyst component has a general formula of R ⁷ _p AlCl
Those represented by _3-p (p ≧ 1.5) are typical (R ⁷ is a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms). Specifically, there are diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride and the like.

(Copolymerization) The copolymerization of the present invention may be carried out by bringing a catalyst into contact with a liquefied olefin or a gas phase olefin, or may be carried out in an inert solvent. Hydrocarbons and chlorinated hydrocarbons are suitable as inert solvents. For example, saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decahydronaphthalene, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and tetrahydronaphthalene. , Chlorobenzene, chlorinated hydrocarbons such as ethylene dichloride. Also,
Hydrocarbon mixtures such as kerosene, petroleum benzene and petroleum ether can also be used.

Hydrogen, alkyl halide, etc., which are known as molecular weight regulators during olefin polymerization, can be present in the copolymerization system. The polymerization conditions are generally the same as in the case of olefin polymerization using a coordination catalyst,
For example, the temperature and pressure are arbitrarily selected depending on the kind of the monomer to be polymerized, the concentration of the catalyst and the desired degree of polymerization, but usually a temperature of 0 to 150 ° C. and a pressure range of 0 to 50 atm are suitable. Is.

The concentration of the TiCl ₃ transition metal catalyst at the time of polymerization may be 0.1 to 500 mmol / liter, preferably 0.3 to 30 mmol / liter in the case of liquid phase polymerization. The molar ratio of the organoaluminum compound as a cocatalyst to titanium trichloride is 1 to 100,
It is preferably 3 to 20. The amount ratio of the polar vinyl monomer and the complex compound of the organic aluminum compound is not particularly limited.

Various modes can be adopted as the method of adding the catalyst component (titanium trichloride and organoaluminum compound) and the polymerization component (olefin and complex compound) in the present copolymerization. For example, a method of preliminarily mixing the complex compound and the organoaluminum compound and then copolymerizing with the olefin, a method of simultaneously supplying the catalyst component and the polymerization component to the polymerization system without premixing, and the like can be adopted. Of course,
The copolymerization is not limited to random copolymerization, but may be a sequential polymerization form in which the polymerization components and proportions are changed during the polymerization. Polymerization can be appropriately performed by a continuous system, a batch system, a semi-continuous system or the like.

After polymerization, the polymer formed with an acid and alcohol, such as hydrochloric acid and isopropanol, to decompose trihydrocarbylaluminum (formula (II)) which may be present in complexed form with the copolymerized polar vinyl monomer. Can be processed.

<Production Polymer> Formed α-Olefin-
The polar vinyl monomer copolymer contains a polar vinyl monomer in an amount of about 0.01 to 30 mol%. The copolymer itself is not only useful as a polar polymer due to the polarity caused by the group Z present therein, but also can be modified into a derivative by focusing on the reactivity of the polar group Z.

[0035]

[Example] [Example 1] 196 mm under a nitrogen gas atmosphere
After ol of 10-undecenoic acid and 196 mmol of triisobutylaluminum were mixed in 300 ml of heptane at room temperature, the solution was reacted under reflux for 1 hour to form a complex compound. After replacing the autoclave with an internal volume of 1 liter with propylene, the total amount of the solution of the complex compound synthesized above was charged, and 41.5 mmol of diethylaluminum chloride was added.
And 1 g of titanium trichloride manufactured by Marubeni Solvay were added in this order. Then, propylene is press-fitted, 65 ℃, 0.2Kg
Polymerization was carried out for 2 hours while maintaining the temperature at / cm ² G. After this, a dry powder was obtained. The powder is isopropanol 30
The mixture was placed in a flask together with 0 ml and 20 ml of concentrated hydrochloric acid, treated at 55 ° C. for 1 hour, and then filtered and dried. The obtained powder was 61 g, and MFR was 0.15 g / 10 minutes.
The content of 10-undecenoic acid was determined by infrared spectroscopy to be 4.
It was 62 mol%.

[Example 2] Polymerization and post-treatment were carried out under the same conditions as in Example 1 except that triethylaluminum for complexing was changed to triethylaluminum. As a result, the obtained powder was 58 g, and the MFR was 7.0 g / 10 minutes. The content of 10-undecenoic acid was 1.7 mol% by infrared spectroscopy.

[Example 3] Polymerization and post-treatment were carried out under the same conditions as in Example 1 except that tri-isobutylaluminum for complexing was changed to tri-n-butylaluminum. As a result, the obtained powder is 102 g, M
FR was 0.1 g / 10 minutes. The content of 10-undecenoic acid was 1.8 mol% by infrared spectroscopy.

Example 4 Polymerization and post-treatment were carried out under exactly the same conditions as in Example 1 except that 196 mmol of triisobutylaluminum for complexing was changed to 294 mmol and 10-undecenoic acid was changed to 294 mmol of 1-hydroxy-10-undecene. Processed. As a result, the obtained powder was 160 g, and the MFR was 0.05 g / 10 minutes. The content of 1-hydroxy-10-undecene was 3.5 mol% according to NMR analysis.

Comparative Example 1 Polymerization and post-treatment were carried out under exactly the same conditions as in Example 1 except that diethyl aluminum chloride was used instead of triisobutylaluminum for complexing. As a result, the obtained powder was 40 g, and MF
R was 0.2 g / 10 minutes. The content of 10-undecenoic acid was 1.1 mol% by infrared spectroscopy.

[Comparative Example 2] Polymerization and post-treatment were carried out under the same conditions as in Example 1 except that the triisobutylaluminum for complexing was changed to ethylaluminum sesquichloride. As a result, the obtained powder is 46 g,
The MFR was 4 g / 10 minutes. The content of 10-undecenoic acid was 1.05 mol% by infrared spectroscopy.

Comparative Example 3 Polymerization and post-treatment were carried out under the same conditions as in Example 4, except that the triisobutylaluminum for complexing in Example 4 was changed to diethylaluminum chloride. As a result, 100 g of the obtained powder
And the MFR was 0.05 g / 10 minutes. The content of 1-hydroxy-10-undecene was 2.1 mol% by NMR analysis.

[Application Example 1] The following components (1) to (3) were blended in the compositions shown in Table 1 and were mixed at 200 ° C. with a twin screw extruder.
After melt-kneading in to form pellets, injection molding machine "M40A-SJ" manufactured by Meiki Seisakusho is used to perform injection molding at 230 ° C.
A flat plate of 65 mm × 65 mm × 2 mm was obtained. (1) Polypropylene resin The ethylene content is 4% by weight, the bending elastic modulus measured according to JIS-K7203 is 14,000 kg / cm ² , and A
MFR measured according to STM-D1238 is 60g
/ 10 min propylene / ethylene block copolymer.

(2) Ethylene / Propylene Rubber Mooney viscosity ML _{1 + 4} (100 ° C.) is 70 and specific gravity is 0.
Ethylene / propylene / copolymer rubber that is 86. (3) Copolymer of Example 4 The above injection-molded flat plate was washed with trichloroethane vapor for 30 seconds and then coated with an air gun. After completion of baking and drying, the mixture was left at room temperature for 48 hours, and a cross-cut test and a peel strength test were conducted. The specific coating method and evaluation test method are as shown below.

<Coating> Coating was performed using a two-component organic solvent-based urethane coating and a one-component organic solvent-based acrylic coating. Coating method : Each paint was mixed, and the thickness of the coating film was about 40 μm in the cross cut test using an air spray gun.
In the peel strength test, spray coating was performed so that the peel strength was about 100 μm. Thereafter, the two-component organic solvent-based urethane coating was baked and dried at 80 ° C. for 60 minutes, and the one-component organic solvent-based acrylic coating was baked at 100 ° C. for 60 minutes and dried.

<Evaluation of Paint Adhesion> Cross-cut test : Using a single-edged razor, eleven vertical and horizontal parallel lines perpendicular to the surface of the test piece are drawn at 2 mm intervals to make 100 cross-cuts. Cellophane adhesive tape (JIS
Z1522) was sufficiently pressure-bonded, kept at about 30 degrees from the coating surface, and peeled off at once in front, the state of the part surrounded by the grids was observed, and the number of grids that did not peel was recorded.

Peel strength : After treating the upper half of the test piece to prevent the paint from adhering, each paint was applied to a coating film thickness of 100.
It was applied so as to have a thickness of μm, and was baked and dried. A cellophane adhesive tape (eg, width of 24 mm made by Nichiban) is adhered to the entire surface of the test piece, and a cut with a width of 1 cm is made to reach the base material in the vertical direction. The side with no coating film adhered was peeled by hand, and the load was recorded when it was attached to a tensile tester and peeled at a speed of 50 mm / min in the 180 ° direction. In addition, when the coating film was ruptured, it was described as rupture. The results of paint adhesion of the molded product are as shown in Table 1.

[0047]

[Table 1]

[0048]

According to the present invention, an α-olefin polymer containing a high content of polar vinyl monomer and having excellent adhesiveness, printability, hydrophilicity and compatibility in a polymer blend,
The high yield can be obtained as described above in the section "Summary of the Invention".

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08F 226: 02)

Claims (1)

[Claims] 1. A method comprising copolymerizing an α-olefin and a polar vinyl monomer represented by the following formula (I) by a Ziegler type catalyst, wherein the polar vinyl monomer has an equimolar amount or more with active hydrogen of the polar group. An α-olefin polymer complexed with an organoaluminum compound represented by the formula (II), wherein the Ziegler-type catalyst is composed of a titanium trichloride compound and an organoaluminum compound. Manufacturing method. [Chemical 1] (Here, Y is a hydrocarbon group having 3 to 20 carbon atoms, and Z is
Is _{^{-NH 2, -NHR 1, (R}} 1 is a hydrocarbon group having 1 to 20 carbon atoms.) - OH or -COOH, m
Is an integer of 1 to 3. ) AlR ² R ³ R ⁴ (II) (wherein R ² , R ³ and R ⁴ each independently represents an alkyl group or an aryl group.)