JPH05170827A - Unsaturated copolymer - Google Patents

Abstract

PURPOSE:To obtain a highly reactive unsaturated copolymer containing highly efficiently introduced alpha,omega-diene-derived unsaturations as repeating units without forming a gellike by-product by copolymerizing ethylene with a 9 C or higher alpha,omega-diene. CONSTITUTION:Ethylene is copolymerized with a 9 C or higher alpha,omega-diene (e.g. 1,9-decadiene) to obtain an unsaturated copolymer comprising repeating units of formulas I and II (wherein R is a linear or branched bivalent hydrocarbon residue containing at least 5 carbon atoms in the straight part) and having a density of 0.89-0.94g/cm<3>, and an MFR of 0.01-100g/10min and a content of repeating units of formula II of 0.1-10mol%. In this way, a highly reactive unsaturated copolymer containing highly efficiently introduced of alpha,omega-diene- derived unsaturations can be obtained without substantially forming any gellike by-product.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to a copolymer having an unsaturated group. More specifically, the present invention provides
The present invention relates to a copolymer having a suspended unsaturated group, which is obtained by copolymerizing ethylene with an α, ω-diene having 9 or more carbon atoms.

[0002]

2. Description of the Related Art Polyethylene resins generally have excellent chemical resistance, but have poor reactivity and are difficult to chemically modify. In order to solve such a problem, it has been proposed to introduce a suspended unsaturated group by copolymerizing α, internal-diene with ethylene (for example, JP-A-56-30413).

However, since the unsaturated group derived from α, internal-diene has a disubstituted structure, it is difficult to say that the reactivity is sufficient. On the other hand, in the copolymerization of ethylene and non-conjugated α, ω-dienes, α, ω-dienes tend to form a ring structure, and it was difficult to introduce unsaturated groups efficiently in a suspended state.

For example, Journal of American
Chemical Society, Vol. 81, p. 4737 (19)
59), it was reported that a soluble polymer having a ring structure corresponding to the chain length of α, ω-diene and a crosslinked insoluble polymer were formed, and in JP-A-1-501555, 1,5-hexadiene and ethylene were prepared. It has been reported that a cyclopentane structure is formed in the copolymerization with 1,5-hexadiene in the copolymerization of a branched α-olefin and a non-conjugated α, ω-diene in JP-A-1-129007. When α is used as an α, ω-diene, 99% or more has a cyclopentane structure, and when 1,6-heptadiene is used as an α, ω-diene, 95% or more is
Furthermore, 33% when 1,7-octadiene is used
Has been reported to have a ring structure.

Furthermore, since α, ω-dienes are usually highly reactive, gels tend to form when a high concentration of α, ω-dienes is introduced into a copolymer, and a practical polymer is produced. It was difficult.

[0006]

The conventional technique as described above is to obtain a highly reactive unsaturated copolymer into which an unsaturated bond derived from α, ω-diene is efficiently introduced.

[0007]

[Means for Solving the Problems]

<Summary> The inventors of the present invention have conducted intensive studies to obtain an ethylene copolymer having a gel-free and highly reactive unsaturated group, and as a result, found a target unsaturated copolymer without the above-mentioned problems. It was

That is, the unsaturated copolymer according to the present invention comprises the following repeating units (I) and (II), has a density of 0.89 to 0.94 g / cm ³ and an MFR of 0.0.
It is 1 to 100 g / 10 minutes, and the content of the repeating unit (II) is 0.1 to 10 mol%.

[0009]

(Wherein R is a linear or branched, divalent hydrocarbon residue in which the linear portion has at least 5 carbon atoms)

Further, another unsaturated copolymer according to the present invention has the following repeating units (I), (II) and (III).
And has a density of 0.86 to 0.94 g / cm ³ , an MFR of 0.01 to 100 g / 10 minutes, and a content of the repeating unit (I) of 99.4 to 70 mol%.
The content of the repeating unit (III) is 0.5 to 20 mol%, and the content of the repeating unit (II) is 0.1 to 10 mol%.

[0012]

(Wherein R is a linear or branched, divalent hydrocarbon residue in which the linear portion has at least 5 carbon atoms. R ¹ represents 1 to 8 carbon atoms; It is a monovalent hydrocarbon residue.)

<Effect> According to the present invention, the repeating unit (I
As I), a highly reactive unsaturated copolymer in which an unsaturated bond derived from α, ω-diene is introduced with high efficiency can be obtained without substantially containing a by-product gel-like substance.

[Detailed Description of the Invention] Unsaturated Copolymer The unsaturated copolymer according to the present invention is defined by the composition and some physical property values.

1) Composition The unsaturated copolymer according to the present invention is composed of repeating units (I) and (II) or (I), (II) and (III).

[0017] (R and R ¹ are as defined above)

It goes without saying that the repeating units (I) and (II) are residues derived from ethylene and a C ₃ or more α-olefin.

The repeating unit (II) is α, which has 9 or more carbon atoms,
It is a residue derived from ω-diene. The repeating unit (II)
The “straight chain portion” in defining the carbon number of R is R itself when R is straight chain, and side chains are excluded when R is branched. Means a part. In other words, the fact that the straight chain portion of R has at least 5 carbon atoms means that the hydrocarbon chain connecting the olefinic unsaturated bonds at both ends has at least 5 carbon atoms in the shortest chain length. is there.

As the α-olefin having 3 or more carbon atoms, which is optionally used to provide the repeating unit (III),
A straight chain or branched chain can be used, and specifically, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1 -Decene and mixtures thereof can be used. Particularly preferred are those having 3 to 10 carbon atoms.

On the other hand, the number of carbon atoms which gives the repeating unit (II) is 9
As the above α, ω-dienes, linear ones and branched ones can be used. Specifically, for example, 1,8-
Nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 3-methyl-1,9
-Decadiene and the like and mixtures thereof can be used. Those having 9 to 15 carbon atoms are preferable, and those having 10 to 14 carbon atoms are particularly preferable.

The content or content of α, ω-dienes is 0.
01 to 10 mol%, more preferably 0.02 to 5
Mol%, and more preferably 0.05 to 3 mol%. If it is less than 0.01 mol%, the effect of the present invention will not be exhibited, and if it exceeds 10 mol%, a gel will be formed, and it will not be a practically useful resin.

The content of the repeating unit (II) is measured such that one terminal ethylenically unsaturated bond in the repeating unit (II) corresponds to the repeating unit (II). That is, the quantification of the ethylenically unsaturated bond is carried out by quantifying the ethylenically unsaturated bond by ¹³ C-NMR spectrum or by using ¹³ C-NMR spectrum at 908 cm ^-1 of the infrared absorption spectrum corresponding thereto. A calibration curve with the absorbance of is prepared in advance, and the infrared absorption spectrum of each sample is 908 cm
^{Calculated from} the absorption of ^-1 .

The content or content of the optional C ₃ or more α-olefin is preferably 0 to 20 mol%, and more preferably 1.0 to 10 mol%.
It is 15 mol%. If it exceeds 15 mol%, the activity of the catalyst is remarkably reduced and the catalyst residue in the copolymer is increased,
A new detouching process is required, which increases the manufacturing cost.

2) Density The unsaturated copolymer according to the present invention has a density of 0.86-0.
It is of 94 g / cm ³ . The measurement is ASTM D-
According to 1505.

The upper limit of the density is determined by the necessary amount of unsaturated groups. The preferred upper limit is 0.
It is about 935 g / cm ³ .

On the other hand, the lower limit of the density is determined by the α, ω-diene content when the gel is formed and the α-olefin content without significant reduction in the catalytic activity, and the copolymerization of ethylene and α, ω-diene 0.89 g / c when combined
m ³ , and more preferably 0.90 g / cm ³ . Further, in the case of a copolymer of ethylene, α-olefin and α, ω-diene, it is 0.86 g / cm ³ , and more preferably 0.88 g / cm ³ .

3) MFR The MFR of the unsaturated copolymer of the present invention, that is, the melt flow rate is 0.01 to 100 g / 10 minutes. The measurement is according to ASTM D-1238.

The upper limit of MFR is determined in order to improve the mechanical properties of the copolymer, and preferably 50 g.
/ 10 minutes. On the other hand, the lower limit value of MFR is determined in order to improve the workability and moldability of the copolymer, and is preferably 0.05 g / 10 minutes.

2. Preparation of Unsaturated Copolymer The copolymer according to the present invention is generally prepared by subjecting the required monomers to copolymerization conditions. Some consideration must be given to the catalyst used and the polymerization conditions so that the resulting copolymer will have the above-mentioned various physical properties.

1) Catalyst used The catalyst used is a catalyst belonging to the category of the so-called Ziegler type catalyst, and is composed of a combination of a solid catalyst component containing at least Ti, Mg and halogen and an organoaluminum compound. The solid catalyst component is preferably a contact product of the following components (A) to (C).

(A) Titanium compound Examples include Ti halides and alkoxides. Specifically, TiCl ₃ , Ti (O-nC ₄ H ₉ ) Cl ₃ ,
_{Ti (O-nC 4 H 9} ) 2 Cl 2, Ti (O-nC 4 H
_{9) Cl 3, Ti (O} -nC 4 H 9) 4, TiCl 3 ·
1/3 AlCl ₃ and the like. The halogen of the halide is typically chlorine, and the alkoxy group of the alkoxide preferably has about 1 to 8 carbon atoms. Further, as is clear from these examples, those in which the valence of Ti is satisfied by both a halogen atom and an alkoxy group are also included.

(B) Magnesium compound Specific examples of Mg include MgCl ₂ , MgBr ₂ , and Mg (O
_{C 2 H 5) 2, Mg} (OCH 3) 2 , and the like, among others MgCl ₂ is preferred.

(C) Electron Donor In addition to the above components (A) and (B), an electron donor can be used if necessary. Any known electron donor can be used in the present invention, but in general, alcohols, ethers, ketones, esters and the like are preferable and preferred.

Contact Method In general, the components (a), (b) or the components (a) to (c) may be contacted with each other at a temperature range of -50 to 200 ° C. The contact time is usually 10 minutes to 5 hours.

Component (a), (b) or component (a)-
The contact of (c) is preferably carried out with stirring, and the contact of each component can be made more complete by mechanically pulverizing with a ball mill, a vibration mill or the like.

Also, sufficient contact can be carried out by dissolving the solid component (b) in the component (a) or (c) and then depositing it as a solid. Ingredient (a),
The contact of (b) or (a) to (c) may be carried out in the presence of a dispersion medium such as a hydrocarbon (eg, hexane, heptane, etc.) or a halogenated hydrocarbon (eg, n-butyl chloride, chloroform, etc.). it can.

Amount Ratio The amount of each component used may be any amount as long as the effect of the present invention is recognized, but generally, the following range is preferable.

(1) The amount of the titanium compound (a) is 1 × 10 ^-2 to 50, more preferably 0.1 to 10, in molar ratio with respect to the magnesium compound. (2) The amount of the electron donor (C) used is 1 × 10 ⁻² to 50, and more preferably 0.1 to 30 in molar ratio with respect to the magnesium compound (B).

The organoaluminum compound which is the other component of the catalyst used in the present invention includes (a) trialkylaluminum (wherein the alkyl group has about 1 to 8 carbon atoms),
For example, triethylaluminum, triisobutylaluminum, ethylisobutylaluminum, etc., (b) dialkylaluminum chloride (where the alkyl group has 1 carbon atom).
~ 6), for example, diethyl aluminum chloride,
(C) alkylaluminum sesquichloride (alkyl group has about 1 to 6 carbon atoms), such as diisobutylaluminum chloride and ethylmethylaluminum chloride,
Examples thereof include ethylaluminum sesquichloride and isobutylaluminum sesquichloride.

Two or more kinds of these organoaluminum compounds may be mixed and used. The amount of the organic aluminum compound used is 0.1 to 200, preferably 1 to 50, in terms of atomic ratio to Ti in the solid catalyst component.

2) Polymerization Method The copolymerization reaction in the present invention can be carried out in either the liquid phase or the gas phase, but the conditions under which the resulting unsaturated copolymer is uniformly dissolved in the liquid phase It is preferable to carry out below.

This is because the unsaturated copolymer produced in the liquid phase is uniformly dissolved, so that the comonomer distribution of α, ω-dienes and α-olefins becomes uniform, and gelation is unlikely to occur. As a preferred specific example of such a liquid phase method, an inert solvent such as hexane, heptane, octane, decane, dodecane, tetradecane, or kerosene as a reaction medium, or a monomer itself as a reaction medium, The temperature at which the resulting unsaturated copolymer dissolves, that is,
There is a method of performing the copolymerization at a temperature of 100 to 300 ° C, preferably 110 to 280 ° C, more preferably 125 to 270 ° C. The copolymerization pressure is appropriately selected in the range of atmospheric pressure to 2000 atm, but when an inert solvent is used, it is at atmospheric pressure to 100 atm, more preferably atmospheric pressure to 50 atm. When the monomer itself is used as the reaction medium, the pressure is preferably 100 to 2000 atm, more preferably 200 to 1500 atm.

The molecular weight can be adjusted by changing the polymerization temperature, but it is effective to add hydrogen to the polymerization system.

The feed ratio of α, ω-diene to ethylene in the copolymerization is 0.001 to 1.0, preferably 0.002 to 0.5, and more preferably 0.003 in terms of molar ratio.
~ 0.3. When it is less than 0.001, the amount of α, ω-dienes contained in the unsaturated copolymer is small, while
If it exceeds 1.0, gel tends to occur.

[0046]

【Example】

Examples 1-5, Comparative Examples 1-3 Preparation N _{2-substituted} atmosphere stainless pot under 1 liter catalyst component, the apparent volume 0.9 l stainless balls (diameter 1
2.7 mm), and commercially available anhydrous MgCl ₂ 50 g, T
iCl ₃ · 1/3 AlCl ₃ 35g, methyl methacrylate 7.5 _g, the SiCl 4 7.5 g was fed,
Vibration pulverization was performed at an amplitude of 2 mm for 100 hours to obtain a solid catalyst component. This solid catalyst component contained 8.5 wt% Ti.

Into a catalyst preparation tank equipped with a stirrer, which had been replaced with N ₂ , was added 1 liter of sufficiently degassed and dehydrated n-hexane, and then 10 g of the solid catalyst component and diethylaluminum chloride 2
5.4g was added and the Al / Ti molar ratio was set to 12. Next, degassed and dehydrated 1-hexene (44.8 g) was added, and the mixture was stirred at 60 ° C. for 1 hour to obtain a catalyst preparation liquid.

[0048] Polymerization an internal volume of 1.5 liters and equipped with a stirrer autoclave to dehydration purified normal paraffin (manufactured by Nippon Mining (Company) C-
14) 0.6cc and α, ω-diene and α shown in Table 1
-Olefin was fed and the temperature of the polymerization tank was raised to 200 ° C. Then, the above-mentioned catalyst preparation liquid was fed to the polymerization tank so that Ti was 1.5 mg, and the ethylene pressure was 9 kg / cm ^2.
Was polymerized. After 20 minutes, the reaction solution was extracted from the polymerization tank, ethanol was added, and the mixture was dried to obtain a white polymer.

The polymerization activity is calculated by dividing the amount of polymer obtained by the amount of Ti used. The content of α, ω-diene was obtained by pressing a polymer into a 0.5 mm-thick sheet and measuring the absorption at 908 cm ^-1 in the infrared absorption spectrum.

For the fish eyes, a 0.5 mm-thick sheet obtained by pressing is biaxially stretched to form a film having a thickness of 50 μm, and there are 50 or less fish eyes having a diameter of 0.4 mm or more per 1200 cm ^2. (◯), 50 or more were judged as (x).

The gel fraction after electron beam crosslinking was determined by subjecting a 1 mm thick sheet obtained by press molding to electron beam irradiation with a dose of 2.5 Mard using "EPS-705" manufactured by Nisshin High Voltage Co., Ltd. Then, it was extracted in boiling xylene for 10 hours, and the ratio of the insoluble residue to the initial sheet weight was determined.

The graft reaction was carried out as follows.
Unsaturated copolymer 10g xylene 200cc at 100 ℃
10 g of butyl acrylate and 0.06 g of azobisisobutyronitrile (AlBN),
Reacted for hours. After reacting for another 2 hours, AlBN 0.1
2 g was added and the reaction was carried out for 4 hours. After the reaction was completed, 1 liter of acetone was added to precipitate a polymer, which was separated by filtration. The filtered product was further extracted with acetone for 10 hours and then dried to obtain a graft body. 17 in the infrared absorption spectrum of the press sheet of this graft body
The graft ratio was determined from the absorption at 30 cm ^-1 .

[0053]

[Table 1]

[0054]

EFFECTS OF THE INVENTION According to the present invention, a highly reactive unsaturated copolymer in which an unsaturated bond of α, ω-diene is introduced with high efficiency can be obtained substantially without containing a by-product gel. This is the same as described above in the section “Means for solving the problems”.

Claims (2)

[Claims] 1. A repeating unit (I) and (II) having a density of 0.89 to 0.94 g / cm ³ and M
An unsaturated copolymer having an FR of 0.01 to 100 g / 10 minutes and a content of the repeating unit (II) of 0.1 to 10 mol%. (Here, R is a linear or branched, divalent hydrocarbon residue in which the number of carbon atoms in the linear portion is at least 5.) 2. A repeating unit (I), (II) and (III) having a density of 0.86 to 0.94 g / cm ^3.
And the MFR is 0.01 to 100 g / 10 minutes,
The content of the repeating unit (I) is 99.4 to 70 mol%, the content of the repeating unit (III) is 0.5 to 20 mol%, and the content of the repeating unit (II) is 0.1. -10 mol%
An unsaturated copolymer characterized by being: (Here, R is a linear or branched divalent hydrocarbon residue having at least 5 carbon atoms in the linear portion.
R ¹ is a monovalent hydrocarbon residue having 1 to 8 carbon atoms. )