JP2561277B2 - Branched α-olefin copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel branched α-olefin copolymer and a method for producing the same. More specifically,
The present invention is a branched α-olefin copolymer useful as a raw material for general molding, or separation or an optical functional material,
And a method for efficiently producing the same.

[Prior Art] In general, olefin-based copolymers are excellent in moldability, mechanical properties, and electrical properties and are inexpensive, so that those having various structures have been developed so far and widely used in many fields. It is being used and its application is steadily expanding.

With the expansion of such applications, the functions required of olefin-based copolymers have been diversified, and development of copolymers having functions suitable for various application fields has been desired. In particular, recently, new functional materials such as separation membranes and optical transmission fibers have been actively researched, and development of materials suitable for such functional materials is strongly desired.

By the way, as the branched α-olefin copolymer, 4
Copolymers of -methyl-1-pentene and various α-olefins are known. For example, copolymerization of 4-methyl-1-pentene and a linear α-olefin having 5 to 18 carbon atoms in the presence of a mixed catalyst of aluminum dialkyl halide and titanium trichloride (Japanese Patent Publication No. 50-22077). ),
Copolymerization of 4-methyl-1-pentene, 1-hexene, and a linear α-olefin having 7 to 10 carbon atoms in the presence of a mixed catalyst of a transition metal compound and an organometallic compound (JP-A-2000-242160) No. 54-139987) and the like are disclosed.

However, these α-olefin copolymers have 5 to 18 carbon atoms as a monomer component to be copolymerized with 4-methyl-1-pentene which is a branched α-olefin.
The straight-chain α-olefin selected from among the above-mentioned linear α-olefins is used. However, since such a straight-chain α-olefin is generally difficult and expensive to produce, the resulting copolymer becomes expensive. It has the drawback that it cannot escape.

Further, since the olefinic hydrocarbon represented by the general formula (II) was extremely difficult to produce, it was completely unknown what properties the copolymer produced using the olefinic hydrocarbon has.

[Problems to be Solved by the Invention] Under these circumstances, the present invention is an inexpensive α-olefin copolymer which is suitably used as a material for general molding or as a material for separation or optical functional materials. The purpose is to provide a coalesce and a method for efficiently producing the same.

[Means for Solving Problems] The present inventors have previously prepared a compound of the general formula easily by oligomerizing propylene using a specific catalyst. It was found that an olefinic hydrocarbon having a vinyl group at the molecular end represented by the formula (m in the formula is an integer of 1 or more) is obtained, and the polymer and the method for producing the polymer were invented.

As a result of further intensive research to achieve the above-mentioned object, the present inventors have found that the general formula (Wherein R is a branched alkyl group having 3 or more carbon atoms) and a branched α-olefin hydrocarbon represented by the general formula (II) It was found that the object can be achieved by copolymerizing in the presence of the above, and the present invention has been completed based on this finding.

That is, the present invention provides (A) general formula (Wherein R is a branched alkyl group having 3 or more carbon atoms), and (B) a general formula (M in the formula is an integer of 1 or more), and a branched α-olefin copolymer having a weight average molecular weight of 191,000 to 829,000 is provided.

According to the present invention, the α-olefin copolymer has the general formula in the presence of a catalyst containing a transition metal compound and an organometallic compound as main components. (Wherein R has the same meaning as above), a branched α-olefin hydrocarbon represented by the following formula: (M in the formula has the same meaning as described above) and can be produced by copolymerizing with an olefinic hydrocarbon represented by

 Hereinafter, the present invention will be described in detail.

In the present invention, the branched α-olefinic hydrocarbon represented by the general formula (I) used as a raw material monomer is a branched alkyl group having 3 or more carbon atoms, wherein R is a branched alkyl group. The branched group may be any of an alkyl group, a cycloalkyl group, and an aryl group, but is selected from those other than the olefinic hydrocarbon represented by the general formula (II) which is another raw material monomer. Be done. Examples of such compounds include 3-methyl-1-butene, 3-cyclohexyl-1-butene, 3-phenyl-1-butene, 4
-Methyl-1-pentene, 4,4-dimethyl-1-pentene, 3-methyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 5 Examples include 5,5-dimethyl-1-hexene and vinylcyclohexane. These monomers may be used alone or in combination of two or more.

In the present invention, the olefinic hydrocarbon having a vinyl group at the molecular end, which is represented by the general formula (II) and is used as another raw material multimer, is, for example, an organoaluminum compound and a condensation product of water and bis (penta Mixture of propylene low polymers obtained by polymerizing propylene in the presence of a catalyst consisting of an alkyl-substituted cyclopentadienyl compound such as methylcyclopentadienyl) hafnium dichloride or bis (pentamethylcyclopentadienyl) zirconium dichloride Can be obtained by separating the product of dimer or higher.

The organoaluminum compound is not particularly limited and may be, for example, a general formula The one represented by is widely used.

Here, R ¹ , R ² and R ³ are cycloalkyl groups, aryl groups or alkyl groups having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and Y is a halogen atom such as hydrogen atom, chlorine or bromine. And alkoxy groups such as methoxy group and ethoxy group.

Examples of the organoaluminum compound represented by the general formula (III) include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trinormalbutylaluminum, triisobutylaluminum, triamylaluminum, trioctylaluminum and the like. Alkyl aluminum and dimethyl aluminum monochloride, diethyl aluminum monochloride, dipropyl aluminum monochloride, diisopropyl aluminum monochloride, diisobutyl aluminum monochloride, dialkyl aluminum monohalide such as dioctyl aluminum monochloride, ethyl aluminum sesquichloride, diethyl aluminum hydride, dimethyl Aluminum ethoxy , Like diethyl Al um methoxide.

These organoaluminum compounds may be used alone or in combination of two or more, but it is preferable to use at least one trialkylaluminum. Among the trialkylaluminums, trimethylaluminum is particularly suitable.

The water to be reacted with the organoaluminum compound is not particularly limited, and may contain some impurities as long as it does not interfere with the reaction product, that is, the product of aluminoxane. As the water to be reacted, in addition to the direct reaction, for example, water of crystallization in a hydrated salt can be used.

Examples of the aluminoxane obtained by condensing the organic aluminum compound and the water include methylaluminoxane, ethylaluminoxane, propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, amylaluminoxane, and the like, and methylaluminoxane is particularly preferable. Is.

There is no particular limitation on the molecular weight or the preparation method of the condensation product of the organoaluminum compound and water, and for example, the organoaluminum compound and water may be condensed in the low polymerization reaction zone, or in the low polymerization reaction zone. You may react and prepare an organoaluminum compound and water before supplying,
Further, the obtained condensation product may be used by supporting it on a solid support, or the condensation product may depend on another organic aluminum compound.

The alkyl-substituted cyclopentadienyl compound (hereinafter sometimes referred to as cyclopentadienyl compound)
Is a compound represented by the general formula [R _t (C ₅ H _5-t )] _s · M · X _4-s ... (IV) (wherein R is an alkyl group having 1 to 20 carbon atoms, t is 1 to 5). An integer, M is a zirconium atom or a hafnium atom, X is a hydrogen atom, a halogen atom or an alkyl group having 1 to 20 carbon atoms, and s is a real number of 1 to 4).

The alkyl group represented by R or X in the general formula (IV) has 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and an amyl group. , Hexyl group, heptyl group, octyl group, nonyl group, capryl group, undecyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, cetyl group, heptadecyl group, stearyl group,
Examples thereof include a nonadecyl group and an eicosyl group.

The halogen represented by X in the general formula (IV) is not particularly limited, but chlorine is preferred.

The compounding ratio for reacting such a cyclopentadienyl compound with the condensation product of the organoaluminum compound and water is usually adjusted so that the aluminum atom / zirconium atom or hafnium atom ratio is 10 to 5000. Is preferred.

The olefinic hydrocarbon represented by the general formula (I) can be obtained by low-polymerizing propylene in the presence of the catalyst thus prepared, but the reaction temperature at that time is not particularly limited. However, the reaction is usually performed in the range of 20 to 80 ° C. The reaction pressure is also not particularly limited, and the reaction may be carried out under normal pressure, or may be carried out at any pressure, for example, a low pressure of 10 kg / cm ² -G or less.

Furthermore, a solvent can be used in this low-polymerization reaction of propylene. Examples of the solvent include benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, naphthalene, tetralin, butylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, benzylbenzene, dibentylbenzene,
Aromatic hydrocarbons such as dodecylbenzene and biphenyl; 2
-Methylbutane, hexane, 2-methylpentane, 2,2
-Dimethylbutane, 2,3-dimethylbutane, heptane,
Aliphatic hydrocarbons such as octane, 2,2,3-trimethylpentane, isooctane, nonane, 2,2,5-trimethylhexane, decane and dodecane; other cyclohexane,
Decalin, petroleum ether, petroleum benzine, petroleum naphtha,
Examples thereof include ligroin, industrial gasoline and kerosene.

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

The olefinic hydrocarbon represented by the general formula (II) can be obtained by separating a dimer or higher product from the mixture of propylene low polymers thus obtained. Specific examples of such olefinic hydrocarbons include 4,6-dimethyl-1-heptene, 4,6,8-trimethyl-1-nonene and 4,6,8,10-tetramethyl-1-
Undecen etc. can be mentioned. These olefinic hydrocarbons may be used alone or in combination of two or more.

Further, among the branched α-olefins represented by the general formula (I), 4-methyl-1-pentene is obtained as a dimer component of these propylene low polymers.

In the present invention, the thus obtained olefin hydrocarbon represented by the general formula (II) and the branched α-olefin hydrocarbon represented by the general formula (I) are used as transition metal compounds. Copolymerization is carried out in the presence of a catalyst consisting mainly of

Examples of the transition metal compound used as one component of the catalyst include compounds used in Ziegler-Natta catalysts, for example, titanium compounds such as titanium trichloride and titanium tetrachloride; nickel compounds such as nickel chloride; zirconium tetrachloride, and trichloride. Zirconium compounds such as zirconium chloride and zirconium oxychloride, and corresponding hafnium compounds; vanadium compounds such as vanadium trichloride, vanadium tetrachloride and vanadium oxychloride; niobium compounds such as niobium pentachloride and niobium oxychloride; molybdenum chloride; Examples thereof include molybdenum compounds such as molybdenum chloride.

Among these transition metal compounds, titanium compounds such as titanium trichloride and titanium tetrachloride are particularly preferable. The above transition metal compounds may be used alone or in combination of two or more.

The transition metal compound supported on a magnesium compound can be used as a catalyst component.

As the magnesium compound used as this carrier,
For example, MgO, MgCl ₂ , Mg (OR) Cl, Mg (OR) ₂ , Mg (O
H) Cl, Mg (OH) ₂ , MgR ₂ , Mg (OCOR) ₂ (each R is an alkyl group) and the like. In order to support the transition metal compound on these magnesium compounds, both may be reacted by, for example, a co-milling method or a slurry method. At this time, an electron donating substance such as ether, ester, ketone or amine may be added as the third component.

Examples of the organometallic compound which is another component of the catalyst include metals belonging to Groups 1 to V of the periodic table, for example,
Li, Na, K, Rb, Cs, Be, Mg, Zn, Cd, Hg, Al, Ge, S
Compounds such as n, Pb, Ti, Zr, Hf and V can be used. Specific examples of the organometallic compound include alkyl sodium, alkyl lithium, alkyl potassium, alkyl lithium aluminum, dialkyl beryllium, dialkyl magnesium, dialkyl zinc, dialkyl cadmium, dialkyl mercury, tetraalkyl germanium, tetraalkyl tin, tetraalkyl lead, Trihalogenated methyl titanium, phenyl trialkoxy titanium,
Examples thereof include those conventionally used as Ziegler-Natta catalysts such as organoaluminum compounds. Among these, organoaluminum compounds are particularly preferable.

As the organoaluminum compound, various organoaluminum compounds used in the production of the olefinic hydrocarbon represented by the general formula (II) can be used. As a preferred organoaluminum compound,
Examples thereof include triethylaluminum and diethylaluminum monochloride. These organometallic compounds are 1
One kind may be used, or two or more kinds may be used in combination.

The ratio of the transition metal compound and the organometallic compound used is 1: 1 to 1: 1000, preferably 1: 5, in terms of metal atomic ratio.
Or selected in the range of 1: 500.

The polymerization method may be any of a slurry polymerization method, a solution polymerization method, a bulk polymerization method and a gas phase polymerization method, but the slurry polymerization method and the solution polymerization method are preferable from the viewpoint of catalytic activity. A polymerization solvent is usually used in this slurry polymerization method or solution polymerization method. As the polymerization solvent, various solvents such as aromatic hydrocarbons, aliphatic hydrocarbons and other solvents which are used as a solvent in the production of the olefinic hydrocarbon represented by the general formula (II) can be used.

The polymerization temperature is not particularly limited, but is usually 20 to 80 ° C.
The polymerization reaction is carried out at a temperature in the range. This temperature is
If it is lower than 20 ° C, the polymerization reaction may not proceed sufficiently, while if it exceeds 80 ° C, the catalytic activity may be lowered.

Further, this polymerization reaction may be carried out under normal pressure or may be carried out under pressure.
It is preferably kg / cm ² -G or less. If the reaction pressure exceeds 50 kg / cm ² -G, the catalytic activity may decrease.

Next, one example of a suitable method for producing a branched α-olefin copolymer of the present invention will be described. First, a transition metal supported on a required amount of a transition metal compound or a magnesium compound as a catalyst component in a suitable solvent. After the metal compound and the organometallic compound are added and sufficiently contacted, a required amount of the branched α-olefin hydrocarbon represented by the general formula (I) and the general formula (II) are represented. Add olefinic hydrocarbon, temperature 20 ~ 80 ℃, pressure 0 ~ 50kg
By copolymerizing under the condition of / cm ² -G, a desired branched α-olefin copolymer can be obtained.

The copolymer thus obtained has the general formula (A) (Wherein R has the same meaning as described above), and (B) a general formula (M in the formula has the same meaning as described above) and a branched α-olefin copolymer.

In this branched α-olefin copolymer, the molar ratio of the (B) unit to the (A) unit is usually 0.001 or more, and the degree of polymerization thereof is preferably 5 or more. The branched α-olefin copolymer pair can be selected from a wide range of properties, from soft to hard, by appropriately selecting the type of raw material monomer, its usage ratio, the degree of polymerization, and the like.

EFFECTS OF THE INVENTION According to the present invention, a branched α-olefin hydrocarbon as a raw material monomer and an olefin oligomer of a propylene oligomer that can be obtained at low cost are copolymerized in the presence of a specific catalyst. Thereby, a branched α-olefin copolymer having a low production cost can be efficiently produced.

Further, by selecting the type and ratio of use of the raw material monomers, the degree of polymerization, etc., it is possible to produce a copolymer having the properties required for each application.

The branched α-olefin copolymer is useful as a material for films, sheets, filaments, daily necessities, other industrial products, or as a material for separation or optically functional materials.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
The invention is in no way limited by these examples.

(Reference example) Synthesis of olefinic hydrocarbon In a reaction vessel, 200 ml of toluene, 47.4 ml of trimethylaluminum (492 mmol) and 35.5 g of copper sulfate pentahydrate (14
2 mmol) was added, and the reaction was carried out for 24 hours under a stream of argon and at a temperature of 20 ° C.

Copper sulfate was filtered off from the obtained product and toluene was distilled off to obtain 12.4 g of methylaluminoxane.

Here, the obtained methylaluminoxane had a molecular weight of 721 as measured by the benzene freezing point depression method.

Next, in an autoclave with an internal volume of 1, toluene 40
Add 0 ml, 6 mmol of the above methylaluminoxane (aluminum equivalent) and 0.01 mmol of bis (pentamethylcyclopentadieniu) hafnium dichloride, and add 50
The temperature was raised to ° C.

After that, hydrogen was introduced at 1 kg / cm ² -G, then propylene was continuously introduced, and the reaction was carried out at a temperature of 50 ° C. for 4 hours while maintaining a propylene partial pressure of 8 kg / cm ^2. I did.

After completion of the reaction, the product was washed with 150 ml of 3N hydrochloric acid aqueous solution to obtain 181.7 g of a propylene low polymer.

By distilling the obtained propylene low polymer,
Dimer fraction consisting of 4-methylpentene-1 having a purity of 99% or more [boiling point; 53.9 ° C], trimer fraction consisting of 4,6-dimethyl-heptene-1 [boiling point; 129 ° C], 4, Tetramer fraction consisting of 6,8-trimethyl-nonene-1 [boiling point: 189 ° C], 4,6,
A pentamer fraction [boiling point: 230 ° C] consisting of 8,10-tetramethyl-undecene-1 and five components of a hexamer and above were separated.

(Example 1) 100 ml of sufficiently dehydrated and dried heptane, 2 mmol of diethylaluminum monochloride and 1 mmol of titanium trichloride (manufactured by Toyo Stofar Chemical Co., Ltd.) were placed in a polymerization vessel having an internal volume of 500 ml, and then 4- Methyl-1-pentene 9.18 g, 4,6-dimethyl-1-heptene
0.79 g was added and polymerization was carried out at 50 ° C. for 4 hours. After the reaction,
The mixture was decalcified with a hydrochloric acid-methanol mixed solution, washed with methanol, and dried to obtain 8.10 g of a polymer.

Next, this polymer was extracted with heptane using a Soxhlet extractor. The extraction residue was 92.6% by weight, and the content of 4,6-dimethyl-1-heptene units in the polymer was 2 mol%. . The melting point (Tm) was found by DSC measurement at 226 ° C and 236 ° C, and the weight average molecular weight was 44.8 ×.
10 ⁴ , and the number average molecular weight was 4.0 × 10 ⁴ . The results are shown in Table 1.

(Examples 2 to 4, Comparative Example 1) The type of organoaluminum was changed as shown in Table 1,
Further, the same operation as in Example 1 was carried out under the reaction conditions shown in Table 1 to obtain a polymer. The results are shown in Table 1.

(Example 5) (1) Preparation of titanium-containing catalyst component A 200 ml three-necked flask was charged with 100 ml of dry n-heptane and 2.0 g (18 mmol) of magnesium diethoxide and stirred.

Next, 0.53 g (3.5 mmol) of ethyl benzoate was added at room temperature, 34 g (180 mmol) of titanium tetrachloride was further added dropwise, and the reaction was carried out under reflux for 3 hours.

After completion of the reaction, washing with a gradient method using n-heptane was repeated to obtain a solid catalyst component.

When the amount of titanium supported in the obtained solid catalyst component was measured by a colorimetric method, it was 40 mg-Ti / g-support.

(2) Polymerization of olefin In a polymerization reactor having an internal volume of 500 ml, 100 ml of sufficiently dehydrated and dried heptane, and 2.5 mmol of triethylaluminum as a catalyst component, 2.5 mmol of diethylaluminum monochloride, and the titanium-containing solid prepared in (1) above. The amount of titanium in the catalyst component was 1 mmol and then 4
9.35 g of -methyl-1-pentene and 0.73 g of 4,6-dimethyl-1-heptene were added, and the mixture was polymerized at 50 ° C for 2 hours. After completion of the reaction, the mixture was decalcified with a hydrochloric acid-methanol mixed solution, washed with methanol, and dried to obtain 9.30 g of a polymer. The results are shown in Table 1.

(Examples 6 to 8 and Comparative Example 2) 3-methyl-1-butene was used as the branched α-olefin, and the same operation as in Example 1 was performed under the conditions shown in Table 1 to obtain copolymers. It was The results are shown in Table 1.
The copolymer obtained here had no solubility in a solvent and the comonomer content and molecular weight could not be measured. However, the copolymer had a lower melting point than the comonomer-free polymer in Comparative Example 2. there were.

Continuation of the front page (56) Reference JP 63-223010 (JP, A) JP 63-20307 (JP, A) JP 61-233032 (JP, A) JP 57-137306 (JP , A) JP-A-55-90514 (JP, A) JP-A-54-128504 (JP, A) US Patent 4658078 (US, A) UK Patent 2027730 (GB, A) UK Patent 903014 (GB, A)

Claims (2)

(57) [Claims] 1. A general formula (A) (Wherein R is a branched alkyl group having 3 or more carbon atoms), and (B) a general formula (M in the formula is an integer of 1 or more), and a branched α- having a weight average molecular weight of 191,000 to 829,000.
Olefin copolymer. 2. The general formula in the presence of a catalyst containing a transition metal compound and an organometallic compound as main components. (Wherein R is a branched alkyl group having 3 or more carbon atoms), a branched α-olefin hydrocarbon represented by the following general formula: (M in the formula is an integer of 1 or more) and an olefinic hydrocarbon represented by (Wherein R is a branched alkyl group having 3 or more carbon atoms), and (B) a general formula (M in the formula is an integer of 1 or more) and a method for producing a branched α-olefin copolymer having a weight average molecular weight of 191,000 to 829,000.