JPH09104722A - Lowly crystalline random ethylene copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lowly crystalline random ethylene copolymer having a narrow molecular weight distribution, a narrow compositional distribution and excellent transparency, surface nonstickiness and mechanical properties by forming a specified random ethylene copolymer. SOLUTION: This lowly crystalline random ethylene copolymer has the following properties:(i) the ethylene content is 35-85wt.%, (ii) the content of 4-10C α-olefins is 15-65wt.%, (iii) the intrinsic viscosity [η] (in decaline at 135 deg.C) is 0.5-10dl/g, (iv) the molecular weight distribution Mw /Mn (GPC) is below 2.5, (v) the degree of crystallinity (X-ray diffraction method) is 30% or below, (vi) the value B represented by the formula (wherein PE is the molar fraction of ethylene; PO is the molar fraction of the α-olefins; POE is the molar fraction of the α-olefin/ethylene chains based on the total dyad chains) is in the range: 1.05<=B<=2, (vii) no αβ and βγ signals ascribable to the methylene chains between two adjoining tert. carbon atoms in the main chain of the copolymer are observed, and (viii) the content of solubles in boiling methyl acetate is 2wt.% or below.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a low crystalline ethylene random copolymer. More specifically, it relates to a low-crystalline ethylene-based random copolymer having a narrow molecular weight distribution and a narrow compositional distribution, excellent transparency, surface non-adhesiveness and mechanical properties.

[0002]

2. Description of the Related Art Conventionally, low crystallinity ethylene / α-olefin copolymers have been in increasing demand for soft molding applications and various resin modifiers. As a production method thereof, a method is known in which ethylene and α-olefin are copolymerized in the presence of a titanium catalyst composed of a titanium compound and an organoaluminum compound or a vanadium catalyst composed of a vanadium compound and an organoaluminum compound. The low crystalline ethylene / α-olefin copolymer obtained with a titanium-based catalyst generally has a wide molecular weight distribution and composition distribution, and is inferior in transparency, surface non-adhesiveness and mechanical properties. In addition, the low crystalline ethylene / α-olefin copolymer obtained with the vanadium catalyst has a narrower molecular weight distribution and composition distribution than those obtained with the titanium catalyst, and it has transparency, surface non-adhesiveness and mechanical properties. However, they are still insufficient for applications requiring these performances, and there is a need for low crystalline ethylene / α-olefin copolymers with improved performance.

On the other hand, a catalyst comprising a zirconium compound and aluminoxane has recently been proposed as a new Ziegler type olefin polymerization catalyst.

In JP-A-58-19309, the following formula (cyclopentadienyl) ₂ Me R Hal, wherein R is cyclopentadienyl, C ₁ -C ₆ -alkyl, halogen and Me is A transition metal-containing compound represented by a transition metal and Hal is a halogen;
The linear aluminoxane represented by the following formula: Al ₂ OR ₄ (Al (R) -O) _n, wherein R is methyl or ethyl, and n is a number of 4 to 20, or the following formula (Al (R)- -O) _{n + 2,} wherein R and n are as defined above, in the presence of a catalyst consisting of a cyclic aluminoxane represented by and one or two of ethylene and a C ₃ -C ₁₂ α-olefin. A method for polymerizing one or more species at a temperature of -50 ° C to 200 ° C is described. The publication describes that in order to control the density of the polyethylene obtained, the polymerization of ethylene should be carried out in the presence of small amounts of up to 10% by weight of somewhat longer-chain α-olefins or mixtures. .

[0005]

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Here, n is 2 to 40 and R is C ₁ to
A linear aluminoxane represented by the following formula, which is C ₆ -alkyl, and the following formula

[0007]

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[0008] Here, the definition of n and R is the same as described above, and an invention relating to a method for producing a cyclic aluminoxane represented by is described. For example, when methylaluminoxane and a bis (cyclopentadienyl) compound of titanium or zirconium are mixed and olefin polymerization is carried out, 25 g or more of polyethylene can be obtained per 1 g of transition metal and per hour. Have been described.

Japanese Unexamined Patent Publication No. 60-35005 discloses the following formula

[0010]

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Wherein R ¹ is C ₁ -C ₁₀ -alkyl and R ⁰ is R ¹ or is bonded to represent --O--, and the aluminoxane compound of the formula is first reacted with a magnesium compound, Then, the reaction product is chlorinated and further treated with a compound of Ti, V, Zr or Cr to prepare a polymerization catalyst for olefin. The publication describes that the catalyst is particularly suitable for the copolymerization of a mixture of ethylene and C ₃ -C ₁₂ α-olefin.

Japanese Unexamined Patent Publication (Kokai) No. 60-35006 discloses a catalyst system for producing a reactor blend polymer, which comprises mono-, di- or tri-cyclopentadienyl of two or more different transition metals or its derivative (a). And alumoxane (aluminoxane) (b) are disclosed. In Example 1 of the publication, ethylene and propylene are polymerized using bis (pentamethylcyclopentadienyl) zirconium dimethyl and alumoxane as catalysts to give a number average molecular weight of 15,300, a weight average molecular weight of 36,400 and a propylene component. It is disclosed that a polyethylene containing 3.4% was obtained. In Example 2, ethylene and propylene were polymerized using bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride and alumoxane as catalysts to give a number average molecular weight of 2,200 and a weight. A toluene-soluble portion containing a propylene component having an average molecular weight of 11,900 and 30 mol% and a number average molecular weight of 3,000,
A number average molecular weight of 2,400 comprising a weight average molecular weight of 7,400 and a toluene insoluble portion containing 4.8 mol% of a propylene component,
000, a weight average molecular weight of 8,300, and a blend of polyethylene and an ethylene / propylene copolymer containing a propylene component of 7.1 mol% were obtained. Likewise

[0013]

[Outside 2]

Mol% soluble part and molecular weight distribution 3.04
And a blend of LLDPE and an ethylene-propylene copolymer consisting of an insoluble portion of propylene component 2.9 mol%.

JP-A-60-35007 discloses that ethylene alone or with α-olefin having 3 or more carbon atoms and metatheron and the following formula (R-Al-O) _n, wherein R has 1 to 5 carbon atoms. Is an alkyl group, and n is 1
Is to about 20 integer, in cyclic alumoxane or the following formula R (R-Al-O) n AlR 2 where expressed, definitions of R and n are as defined above, in the linear alumoxanes represented A method of polymerizing in the presence of a catalyst system containing is described. According to the description of the publication, the polymer obtained by the method has a weight average molecular weight of about 500 to about 1.4 million and a molecular weight distribution of 1.5 to 4.0.

Further, in JP-A-60-35008, polyethylene or ethylene having a broad molecular weight distribution and ethylene and C ₃ -C ₁₀ α are used by using a catalyst system containing at least two kinds of metacerone and alumoxane. -Olefin copolymers can be produced

[0017]

[Outside 3]

It has been described that

Further, Japanese Patent Laid-Open No. 60-35009 discloses a vanadium compound and an organic aluminum.

[0020]

[Outside 4]

A method for producing a copolymer of ethylene and α-olefin, which is less than or equal to less than, is disclosed.

[0022]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel low crystalline ethylene random copolymer.

Another object of the present invention is to provide an ethylene-based random copolymer having a narrow molecular weight distribution and compositional distribution, excellent transparency, surface non-adhesiveness and mechanical properties, and low crystallinity.

Still another object of the present invention is to provide a low crystalline ethylene-based random copolymer which, when blended with a thermoplastic resin, gives a composition excellent in impact resistance, particularly low temperature impact resistance.

Still another object of the present invention is to provide a low crystalline random copolymer which, when blended with a thermoplastic resin, gives a composition having excellent heat sealability.

Still another object of the present invention is to provide a low crystalline random copolymer which, when blended with a thermoplastic resin, gives a composition having excellent transparency.

Still another object of the present invention is to provide a method for producing the low crystalline ethylene random copolymer of the present invention and its use as a compounding agent for thermoplastic resins.

Further objects and advantages of the present invention will be apparent from the following description.

[0029]

According to the present invention, the low crystallinity ethylene-based random copolymer of ethylene and α-olefin having 3 to 20 carbon atoms is used. (A) the content of the ethylene component is in the range of 35 to 85% by weight, and the content of the α-olefin component is in the range of 15 to 65% by weight, (b) in decalin at 135 ° C. Intrinsic viscosity [η] measured in the range of 0.5 to 10 dl / g,

[0030]

[Outside 5]

(D) The crystallinity determined by the X-ray diffraction method is 30% or less, and (e) the following formula (I).

[0032]

(Equation 2)

[Wherein P _E represents the mole fraction of the ethylene component in the copolymer, P _O represents the mole fraction of the α-olefin component, and P _OE represents the α-olephine of the entire dyad chain. B shows the molar fraction of ethylene chain] in the range satisfying the following formula (II) 1.05 ≦ B ≦ 2 (II), and (f) ¹³ C-NMR spectrum shows , Αβ and βγ signals based on a methylene chain between two adjacent tertiary carbon atoms in the main chain of the copolymer are not observed, and (g) the boiling methyl acetate soluble part is 2.0% by weight or less. A low crystallinity ethylene-based random copolymer characterized by:

The low crystalline ethylene random copolymer of the present invention is, according to the present invention, (A) a zirconium hydride compound having a group having a conjugated π electron as a ligand, and (B) an aluminoxane. It can be produced by the method of the present invention in which ethylene is copolymerized with α-olefin having 3 to 20 carbon atoms in the presence of a catalyst consisting of

The zirconium hydride compound (A) having a ligand having a group having a conjugated π electron is, for example, a compound represented by the following formula (III) R ¹ R ² R ³ ZrH (III) where R ¹ is a cycloalkadienyl group. And R ² and R ³ are cycloalkadienyl groups, aryl groups, alkyl groups, halogen atoms or hydrogen atoms.

The cycloalkadienyl group is, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl group or a tetrahydroindenyl group. Examples of the alkyl group of R ² and R ³ include a methyl group, ethyl group, propyl group, isopropyl group, butyl group and the like, and examples of the aryl group include a phenyl group, a benzyl group, a neofoyl group and the like. The halogen atom can be fluorine, chlorine,
Examples thereof include bromine. Examples of the zirconium hydride compound include the following compounds.

Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methyl zirconium hydride, bis (cyclopentadienyl) ethyl zirconium hydride , Bis (cyclopentadienyl) cyclohexyl zirconium hydride, bis (cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (methyl Cyclopentadienyl) zirconium monochloride monohydride, bisindenyl zirconium monochloride monohydride, above The ruconium hydride compound can be used as it is, but a compound such as bis (cyclopentadienyl) zirconium monochloride monohydride which is poorly soluble in a solvent such as toluene is used after contacting with an organoaluminum compound. It is preferable. By this operation, the solvent-insoluble zirconium hydride compound can be made easily soluble in the solvent.

Specific examples of the organoaluminum compound to be brought into contact with the zirconium hydride compound include trialkylaluminums such as trimethylaluminum, triethylaluminum and tributylaluminum, trialkenylaluminums such as triisoprenylaluminum, dimethylaluminum methoxide and diethyl. In addition to dialkyl aluminum alkoxides such as aluminum ethoxide and dibutyl aluminum butoxide, alkyl aluminum sesquialcosides such as methyl aluminum sesquimethoxide and ethyl aluminum sesquiethoxide, the average composition represented by R ¹ _2.5 Al (OR ² ) _0.5, etc. Partially alkoxylated alkylaluminum with, dimethylaluminium chloride, diethylaluminium Partially halogenated dialkyl aluminum halides such as mu chloride, dimethyl aluminum bromide, alkyl aluminum sesquichlorides such as methyl aluminum sesquichloride, alkyl aluminum sesqui chlorides such as methyl aluminum sesquichloride, alkyl aluminum dihalides such as methyl aluminum dichloride and ethyl aluminum dichloride. Examples thereof include alkyl aluminum and the like.

The reaction between the two compounds is preferably carried out in a hydrocarbon medium, with or without light, and the mixing molar ratio (Al / Zr) of the organoaluminum compound and the zirconium compound is 0.1.
The concentration of zirconium is 5 to 30, preferably 1 to 20, and the concentration of zirconium is 0.001 to 1 mol per liter of liquid phase, preferably 0.0.
The reaction temperature is 0 to 120 ° C.
It is sufficient to bring both into contact with each other. The hydrocarbon medium can be selected from those exemplified as the solvent for polymerization described later.

Specific examples of the aluminoxane (B) as a catalyst constituent used in the method of the present invention include general formula (IV) or general formula (V).

[0041]

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An organic aluminum compound represented by the formula (wherein R represents a hydrocarbon group, m preferably represents an integer of 20 or more, and particularly preferably an integer of 25 or more) can be exemplified. In the aluminoxane, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group, and m is preferably 20 or more. It represents an integer, particularly preferably an integer of 25 or more, particularly preferably an integer of 30 to 100. The following method can be exemplified as a method for producing the aluminoxane.

(1) Compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, etc. Method of adding and reacting.

(2) A method in which water is allowed to directly act on a trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

Of these methods, the method (1) is preferably adopted. The aluminoxane may contain a small amount of an organic metal component.

In the method of the present invention, the raw materials supplied to the polymerization reaction system are ethylene and 3 to 20 carbon atoms other than ethylene.
Of α-olefin. The content of ethylene in the polymerization raw material olefin is usually 10 to 90 mol%, preferably 20 to 80 mol%, and the content of the α-olefin is usually 10 to 90 mol%, preferably 20 to 80 mol%. It is a range.

As the α-olefin having 3 to 20 carbon atoms other than ethylene used as a raw material for polymerization in the method of the present invention, specifically, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-
Examples thereof include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

In the process of the present invention, the olefin polymerization reaction is usually carried out in a hydrocarbon medium. Specific examples of the hydrocarbon medium include butane, isobutane, pentane,
Hexane, octane, decane, dodecane, hexadecane, octadecane and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane and other alicyclic hydrocarbons, benzene, toluene, xylene and other aromatic hydrocarbons In addition to petroleum fractions such as hydrogen, gasoline, kerosene, and light oil, the raw material olefin is also a hydrocarbon medium. Of these hydrocarbon media, aromatic hydrocarbons are preferred.

In the method of the present invention, a liquid phase polymerization method such as a suspension polymerization method or a solution polymerization method is usually adopted, and a solution polymerization method is particularly preferably adopted. The temperature during the polymerization reaction is -50 to 200 ° C, preferably -30 to 10
0 ° C, particularly preferably in the range of -20 to 80 ° C.

The ratio of the zirconium hydride compound (A) used when the method of the present invention is carried out by the liquid phase polymerization method is usually 10 ⁻⁸ to 10 ⁻² g as the concentration of zirconium metal atom in the polymerization reaction system. Atom / l, preferably in the range of 10 ⁻⁷ to 10 ⁻³ gram atom / l. The aluminoxane content is usually 10 ^-4 to 10 ^-1 as the concentration of aluminum atoms in the polymerization reaction system.
Gram atom / l, preferably in the range of 10 ^-3 to 5 × 10 ^-2 gram atom / l, and the ratio of aluminum metal atom to zirconium metal atom in the polymerization reaction system is usually 25 to 10 ⁷ , preferably 10 ² to 10
It is in the range of ⁶ . The molecular weight of the copolymer can be adjusted by hydrogen and / or the polymerization temperature.

In the method of the present invention, the low crystallinity ethylene-based copolymer of the present invention can be obtained by treating the polymerization reaction mixture after completion of the polymerization reaction by a conventional method.

The composition of the low crystalline ethylene copolymer of the present invention has an ethylene component of 35 to 85% by weight, preferably 40 to 80% by weight, and the α-olefin component of 15 to 65% by weight, preferably 20 to 40% by weight. It is in the range of 60% by weight.

The low crystalline ethylene random copolymer of the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.5 to 10 dl / g, preferably 1 to 6 dl / g. Has a value in the range of g.

The low crystalline ethylene copolymer has a molecular weight distribution (Mw / Mn) of 2.5 or less measured by gel permeation chromatography (GPC).
The range is preferably 2.3 or less, and particularly preferably 2 or less. When the molecular weight distribution of the low crystalline ethylene-based copolymer is more than 2.5, the copolymer or the composition containing the copolymer as a modifier becomes too sticky or becomes blocked. Therefore, it is necessary to be within the above range.

The low crystallinity ethylene copolymer has a low crystallinity, and its crystallinity determined by X-ray diffraction is 30.
% Or less, preferably 20% or less, particularly preferably 0 to 15%.

[0056]

[Outside 6]

According to "Romatographie", the procedure is as follows.

(1) Using standard polystyrene of known molecular weight (Toyo Soda (manufactured by Toyo Soda) monodisperse polystyrene),
Molecular weight M and its GPC (Gel Permeation Chromatograp
h) Count and measure the molecular weight M and EV (Elution Volum
e) Create a correlation diagram calibration curve. The concentration at this time is 0.0
2% by weight.

(2) GPC chromatograph of the sample is taken by GPC measurement, and by the above (1)

[0060]

[Outside 7]

Find the value. The sample preparation conditions and GPC measurement conditions at that time are as follows.

[Preparation of sample] (a) A sample is put into an Erlenmeyer flask together with an O-dichlorobenzene solvent so as to be 0.1% by weight.

(B) The antioxidant, 2,6-di-tert-butyl-P-cresol, is added to the Erlenmeyer flask containing the sample in an amount of 0.05% by weight based on the polymer solution.

(C) The Erlenmeyer flask is heated to 140 ° C. and stirred for about 30 minutes to dissolve it.

(D) The filtrate is applied to GPC.

[GPC measurement conditions] The measurement was carried out under the following conditions.

(A) Device manufactured by Waters (150C
-ALC / GPC) (b) Column manufactured by Toyo Soda (GMH type) (c) Sample amount 400 μl (d) Temperature 140 ° C. (v) Flow rate 1 ml / min Furthermore, the low crystalline ethylene copolymer of the present invention is Formula (I) below

[0068]

(Equation 3)

[Wherein, P _E represents the content mole fraction of the ethylene component in the copolymer, P _O represents the content mole fraction of the α-olefin component, and P _OE represents the α-olephine of the entire dyad chain. B value represented by [indicating mole fraction of ethylene chain] is in a range satisfying the following formula (II) 1.05 ≦ B ≦ 2 (II).

The B value is an index showing the distribution state of each monomer component in the copolymer chain. J. Ray
(Macromolecules, 10 , 773 (19
77)); C. Randall (Macromol
ecules, 15 , 353 (1982), J. Am. Pol
ymer Science, Polymer Phys
ics Ed. , 11 , 275 (1973)), K.S. K
imura (Polymer, 25 , 441 (198
4)) Based on the report of et al., It is calculated by _obtaining P _E , P _o and P _OE defined above. The larger the B value, the smaller the number of block-like chains, the more uniform the distribution of ethylene and α-olefin, and the more the composition is narrow.

The low crystalline ethylene copolymer of the present invention is
It preferably has the following B value.

When the ethylene content of the copolymer is 50 mol% or less: 1.0 + 0.3 × P _E ≦ B ≦ 1 / (1-P _E ), more preferably the general formula 1.0 + 0.4 × P _E ≦ B ≦ 1 / (1-P _E ), particularly preferably the general formula 1.0 + 0.5 × P _E ≦ B ≦ 1 / (1-P _E ), when the ethylene content of the copolymer is 50 mol% or more. : 1.3-0.3 × P _E ≦ B ≦ 1 / P _E , more preferably the general formula 1.4-0.4 × P _E ≦ B ≦ 1 / P _E , particularly preferably the general formula 1.5. −0.5 × P _E ≦ B ≦ 1 / P _E , the composition distribution B value is about 20 in a 10 mmφ sample tube.
The ¹³ C-NMR spectrum of a sample in which 0 mg of the copolymer was uniformly dissolved in 1 ml of hexachlorobutadiene,
Usually, measurement temperature 120 ℃, measurement frequency 25.05MH
z, spectrum width 1500 Hz, filter width 1500
Hz, pulse repetition time 4.2sec, pulse width 7μ
It was calculated by measuring P _e , P _o , and P _OE from this spectrum by measuring under the measurement conditions of sec and the number of integration of 2000 to 5000 times. Furthermore, in the ¹³ C-NMR spectrum of the low crystalline ethylene copolymer of the present invention, αβ and βγ signals based on a methylene chain between two adjacent tertiary carbon atoms in the main chain of the copolymer. Is not observed.
For example, in a copolymer of ethylene and 1-hexene,
Combine the following:

[0073]

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When viewed from the tertiary carbon on the left side derived from 1-hexene, the three central methylene groups are α from the left side,
It is located at β and γ positions, while it is located at α, β, and γ positions from the right when viewed from the tertiary carbon on the right side. Therefore, there is a methylene group giving the signals of αγ and ββ in the above binding unit, but no methylene group giving the signals of αβ and βγ.

Similarly, 1-hexene comrades bound head to tail were:

[0076]

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In the above, only a methylene group giving an αα signal is present, and no methylene group giving an αβ signal and a βγ signal is present.

On the other hand, the following combination

[0079]

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Each has a methylene group that provides a βγ signal and an αβ signal. From the above description, it is clear that the low crystalline ethylene-based copolymer of the present invention has a regular bonding direction of a monomer copolymerizable with ethylene.

The boiling crystalline methyl acetate-soluble content of the low crystalline ethylene random copolymer of the present invention is 2% by weight or less, preferably 1.5 to 0.01% by weight, particularly preferably 1.0.
-0.03% by weight, particularly preferably 0.7-0.0%
It is in the range of 5% by weight. When the weight fraction P _EW ethylene component units of the low crystalline ethylene-based random copolymer, the boiling methyl acetate-soluble content of the low crystalline ethylene-based random copolymer [E _X wt%] is preferably is preferably from E _X ≦ 2.2-2 × P _EW particularly preferably E _X ≦ 1.35-P _EW in the range of E _X ≦ 0.9-0.6 × P _EW.

For the measurement of the amount of boiling methyl acetate extracted, 1 sample was used.
After making a press sheet with a thickness of mm, this press sheet was cut into 2 mm × 2 mm square pieces and put in a cylindrical glass filter, and the reflux frequency was set to about 1/5 minutes, and the soxhlet extractor was performed for 6 hours. . The extraction amount was determined by drying the rest of the extraction with a vacuum dryer until a constant weight was obtained.

The low crystalline ethylene random copolymer of the present invention usually has a density of 0.90 g / cc or less. The stress at break and the elongation at break are 300 kg each.
/ Cm ² or less and 400% or more. The density was measured after the sample was heat-treated at 120 ° C. for 1 hour and gradually cooled to room temperature over 1 hour. The stress at break and the elongation at break are ring-shaped test pieces (inner diameter 18 mm, outer diameter 22 mm, thickness 1 m
m) was prepared and measured at a tensile speed of 500 mm / min and a measurement temperature of 25 ° C.

The low crystalline ethylene random copolymer of the present invention has a narrower molecular weight distribution and composition distribution and is transparent, surface non-adhesive and It can be said that it has excellent mechanical properties. Further, it can be said that the molecular weight distribution and the composition distribution are almost the same or narrower than that of the copolymer obtained by using the vanadium-based catalyst, but the arrangement state of the copolymerization component in the molecular chain is different.

The low crystalline ethylene random copolymer of the present invention can be blended with various thermoplastic resins as a modifier thereof.

By blending the low crystalline ethylene random copolymer of the present invention with another ethylene polymer containing ethylene as a main component, such as polyethylene, the impact resistance of the other ethylene polymer, particularly at low temperature. An ethylene polymer composition having improved impact resistance, bending resistance, and low temperature heat sill resistance is obtained, and the ethylene polymer composition has a transparency and a surface by blending a low crystalline ethylene random copolymer. It is characterized in that it does not reduce non-stickiness. Examples of the other ethylene-based polymers include high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1 −
Dodecene, 1-tetradecene, 1-hexadecene, 1-
Examples thereof include copolymers with α-olefin having 3 to 20 carbon atoms such as octadecene and 1-eicosene, and ethylene-based copolymers containing ethylene as a main component. The intrinsic viscosity [η] measured in decalin at 135 ° C. is usually in the range of 0.5 to 20 dl / g.

When the low crystalline ethylene random copolymer of the present invention is blended with the other ethylene polymer, the blending ratio is usually 0.5 to 100 parts by weight of the other ethylene polymer. It is in the range of 30 parts by weight, preferably 1 to 20 parts by weight. The resulting ethylene-based polymer composition, if necessary, an antioxidant, a hydrochloric acid absorbent, an anticoagulant, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather resistance stabilizer, an antistatic agent, a nucleating agent, a pigment, Various additives such as a filler can also be blended. The mixing ratio is appropriate. The ethylene polymer composition can be prepared according to a conventionally known method.

Further, the low crystalline ethylene random copolymer of the present invention is blended with a crystalline olefin polymer other than the other ethylene polymers to obtain a molded product of the crystalline olefin polymer. The impact resistance, especially at low temperature, and the addition of the low crystalline ethylene random copolymer does not bring about a decrease in transparency and surface non-adhesiveness. Specific examples of the crystalline olefin polymer other than the ethylene polymer include polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-1-hexene, and propylene ethylene. Copolymer, propylene / 1-butene copolymer, 1-
Propylene, 1-butene, 1-hexene and other α-olefins (a ₁ ) and ethylene, propylene, 1-butene, 1-hexene, such as butene / ethylene copolymer and 1-butene / propylene copolymer. , 4-methyl-1-
Pentene, 1-octene, 1-decene, 1-dodecene,
1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like, α-olefins having 2 to 20 carbon atoms, which are different from the α-olefin (a ₁ ) and α-olefin (a ₂ ). Crystalline α-
An olefin-based copolymer can be exemplified. The intrinsic viscosity [η] of the crystalline olefin polymer measured in decalin at 135 ° C. is usually 0.5 to 10 dl / g.
And the crystallinity is 5% or more, preferably 20% or more.

When the low crystalline ethylene random copolymer of the present invention is blended with the crystalline α-olefin polymer, the blending ratio is 100% of the crystalline α-olefin polymer.
It is usually in the range of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight with respect to parts by weight. The crystalline α-olefin polymer composition may optionally contain an antioxidant,
Hydrochloric acid absorber, anti-agglomeration agent, heat stabilizer, UV absorber,
Various additives such as a lubricant, a weather resistance stabilizer, an antistatic agent, a nucleating agent, a pigment and a filler can also be added. The crystalline α-
The olefin polymer composition can be prepared according to a conventionally known method.

Furthermore, by blending the low crystalline ethylene random copolymer of the present invention with various engineering resins, the physical properties of the engineering resin, such as impact resistance and sliding characteristics, can be improved, In addition, the blending of the low crystalline ethylene random copolymer is characterized in that the transparency and the surface non-tackiness are not lowered. When the engineering resin is an engineering resin having a polar group, in order to improve the affinity or dispersibility to the engineering resin, the low crystalline ethylene random copolymer of the present invention, maleic acid, Modified ethylene-based random copolymers obtained by graft-copolymerizing unsaturated carboxylic acids such as citraconic acid, itaconic acid, maleic anhydride, citraconic acid anhydride, itaconic anhydride, dimethyl maleate, dimethyl citraconate, and dimethyl itaconic acid derivatives. Preference is given to using coalescence. The graft ratio of the unsaturated dicarboxylic acid or its derivative component is usually in the range of 0.02 to 50 parts by weight with respect to 100 parts by weight of the low crystalline ethylene random copolymer. Specifically as the engineering resin, polyethylene terephthalate, polyester such as polybutylene terephthalate, hexamethylene adipamide, octamethylene adipamide, decamethylene adipamide, dodecamethylene adipamide, polycaprolactone,
Polyamide such as, polyarylene oxide such as polyphenylene oliside, polyacetal, ABS, AE
S, polycarbonate and the like can be exemplified. The blending ratio of the low crystalline ethylene random copolymer or its modified product is usually in the range of 0.2 to 20 parts by weight with respect to 100 parts by weight of the engineering resin. The engineering resin composition may contain an antioxidant,
Hydrochloric acid absorber, anti-agglomeration agent, heat stabilizer, UV absorber,
Various additives such as lubricants, weather resistance stabilizers, antistatic agents, nucleating agents, pigments and fillers can be added. The engineering resin composition can also be prepared according to a conventionally known method.

The low crystalline ethylene random copolymer of the present invention can be mixed with various rubber-like polymers to improve the physical properties of the rubber-like polymer, such as chemical resistance and rigidity. Specifically as the rubber-like polymer,
Examples thereof include ethylene / propylene / non-conjugated diene copolymer, ethylene / 1-butene / non-conjugated diene copolymer, polybutadiene rubber, polyisoprene rubber, and styrene / butadiene / styrene block copolymer. The blending ratio of the low crystalline ethylene random copolymer is usually in the range of 1 to 100 parts by weight based on 100 parts by weight of the rubber-like polymer. If necessary, various fillers such as a filler, a cross-linking agent, a cross-linking aid, a pigment and a stabilizer can be added to the rubber-like polymer composition. The rubbery polymer composition can be prepared according to a conventionally known method.

[0092]

Next, the method of the present invention will be specifically described with reference to examples.

Example 1 Preparation of Zirconium Catalyst A 100 ml glass flask thoroughly purged with nitrogen was charged with 30 ml of toluene and 2 mmol of bis (cyclopentadienyl) zirconium monochloride monohydride to form a slurry. 20 mmol of trimethylaluminum (1M solution) diluted with toluene was added dropwise thereto at room temperature. After the dropping was completed, the temperature was raised to 60 ° C. and the reaction was performed for 1 hour. Bis (cyclopentadienyl) zirconium monochloride monohydride was dissolved in toluene and the solution became dark red. The above reaction was carried out by cutting off light.

Preparation of Methylaminooxane To a 400 ml glass flask sufficiently purged with argon were charged 13.9 g of magnesium chloride hexahydrate and 125 ml of toluene, and after cooling to 0 ° C., 125 m of toluene was added.
250 mmol of trimethylaluminum diluted with 1 was added dropwise. After dropping, the temperature was raised to 70 ° C.
The reaction was performed for 6 hours. After the reaction, solid-liquid separation was performed by filtration, and toluene was removed from the separated liquid under reduced pressure to obtain 7.3 g of white solid methylaluminoxane. The molecular weight determined by freezing point depression in benzene is 1910.
And the m-value of the aluminoxane was 31.
During the polymerization, the aluminoxane was redissolved in toluene before use.

Polymerization Using a continuous polymerization reactor of 2 liters, purified toluene was 2 liters / hr, methylaluminoxane was 10 mg / aluminum in terms of aluminum atom, and the zirconium catalyst prepared above was 1 liter in terms of zirconium atom. × 1
Continuously fed at a rate of 0 ^-2 mg atom / hr, and simultaneously fed with 360 liter / hr of ethylene in the polymerization vessel,
One butene was continuously fed at a rate of 240 liter / hr, and the polymerization was carried out under the conditions that the polymerization temperature was 20 ° C., the atmospheric pressure was the residence time was 0.5 hours, and the polymer concentration was 36 g / liter. The produced polymer solution was continuously withdrawn from the polymerization vessel, the polymerization was stopped by adding a small amount of methanol, the polymer solution was transferred into a large amount of methanol, and the precipitated polymer was dried under reduced pressure at 130 ° C. for 12 hours.

[0096]

[Outside 8]

Crystallinity 2.1%, B value 1.14, density 0.
A rubber-like polymer having 888 g / cm ³ and a boiling methyl acetate extraction amount of 0.31% by weight was obtained. The stress at break and the elongation at break of this polymer were 110 kg / cm ² and 9 respectively.
00%. ¹³ C-NMR of the obtained polymer
No signals based on αβ and βγ were observed in the spectrum. The activity per unit zirconium is 7300g
-Polymer / milligram atom-Zr.

Examples 2 to 8 and Comparative Example 1 The procedure of Example 1 was repeated except that the polymerization was conducted under the conditions shown in Table 1. In the ¹³ C-NMR spectrum of the obtained polymer, no signals based on αβ and βγ were observed. The results are shown in Table 1.

Comparative Example 2 Tetrabutoxytitanium 2 was placed in an 800 ml SUS pot containing 2.8 kg SUS balls (15 mmφ).
g and 20 g of anhydrous magnesium chloride were put therein, and the mixture was ground for 8 hours in a nitrogen atmosphere (vibration mill). The co-ground product was transferred into 200 ml of ethylene dichloride and heated at 80 ° C. for 2 hours. Thereafter, the co-ground product was filtered off and washed with n-decane until no free titanium tetrachloride was detected. 21 g of titanium atoms were supported on 1 g of the catalyst thus obtained.

Polymerization Using the same polymerization reactor as in Example 1, purified decane was 2 liters / hr, ethylaluminum sesquichloride was 8 mg atom / hr in terms of aluminum atom, and the titanium catalyst prepared above was titrated in terms of titanium atom. It is continuously fed at a rate of 0.4 mg atom / hr, and is continuously fed at a rate of 300 liter / hr of ethylene and 100 liter / butene of 100 liter / hr at the same time in the polymerization system. Polymerization was carried out under the conditions of pressure, residence time of 0.5 hours and polymer concentration of 50 g / liter. The subsequent operation was performed according to Example 1. No signals based on αβ and βγ were observed in the ¹³ C-NMR spectrum of the obtained polymer. Table 2 shows the results.

Comparative Example 3 Using the same polymerization reactor as in Example 1, 2 parts of purified hexane was used.
L / hr Ethyl aluminum sesquichloride was continuously supplied at a rate of 1 mg atom / hr in terms of aluminum atom, and vanadyl trichloride was 0.1 mg atom / hr in terms of vanadium atom, and 200 liters of ethylene were simultaneously fed in the polymerization vessel. / Hr, propylene 240 liters / hr at a rate of continuous feeding, polymerization temperature 50
Polymerization was carried out under conditions of a temperature of 0 ° C., atmospheric pressure, a residence time of 0.5 hours, and a polymer concentration of 4 g / liter. The subsequent operations were exactly the same as in Example 1. ¹³ C-of the obtained polymer
In the NMR spectrum, unlike in Examples 1 to 8, αβ and β
A signal based on γ was observed. Table 3 shows the results.

Comparative Examples 4 to 6 The same procedure as in Comparative Example 3 was carried out except that the polymerization was conducted under the conditions shown in Table 3. In the ¹³ C-NMR spectrum of the obtained polymer, signals based on αβ and βγ were observed as in Comparative Example 3. Table 3 shows the results.

Application Examples 1 to 5 Comparative Application Examples 1 to 6 Ethylene random copolymer and polyethylene resin (MFR 0.44 g / 10 min,
A density of 0.959 g / cm ³ ) was melt-mixed at a ratio of 1: 9, and then a press film having a thickness of 70 μ was prepared (1
80 ° C, 5 minutes preheat → degassing 30 seconds → 30 kg / cm ²
Pressurization, hold for 4 minutes 30 seconds → cold press at 20 ℃, 50k
g / cm ² pressurization for 3 minutes). About this film 23
The film impact strength and the transparency (haze value) at C and -20 C were measured. Table 4 shows the results.

Application Example 6 Comparative Application Examples 7 to 9 The ethylene random copolymers of the above Examples and Comparative Examples were melt mixed with a polypropylene resin (MFR 10 g / 10 min) at a ratio of 1: 9, and then pressed with a thickness of 30 μ. A film was prepared (similar to Application Example 1). The film impact strength and transparency (haze value) at 23 ° C. of this film were measured. Table 5 shows the results.

Example 11 Preparation of zirconium catalyst The same procedure as in Example 1 was carried out except that trin-octylaluminum was used in place of the trimethylaluminum used in Example 1.

Polymerization Using a polymerization reactor similar to that used in Example 1, 1 part of purified toluene was used.
Liter / hr Methylaluminoxane synthesized in the same manner as in Example 1 at a ratio of 5 mg atom / hr in terms of aluminum atom, and the zirconium catalyst prepared above at a rate of 1 × 10 ^-2 mg atom / hr in terms of zirconium atom. Continuously feed and simultaneously ethylene 360 liters / hr and propylene 240 liters / h in the polymerization vessel.
r and 1,4-hexadiene were continuously fed at a rate of 2 g / hr, polymerization temperature was 20 ° C., normal pressure, residence time was 1 hour,
Polymerization was carried out under the condition that the polymer concentration was 20 g / liter. The subsequent operations were exactly the same as in Example 1. Ethylene content 70% by weight,

[0107]

[Outside 9]

A density of 0.871 g / cm ³ , an iodine value of 9,
A rubbery polymer having a boiling methyl acetate extraction of 0.38% by weight was obtained. In the ¹³ C-NMR spectrum of this polymer, no signals based on αβ and βγ were observed. The activity per unit zirconium was 2000 g-polymer / milligram atom-Zr.

[0109]

[Table 1]

[0110]

[Table 2]

[0111]

[Table 3]

[0112]

[Table 4]

[0113]

[Table 5]

[0114]

[Table 6]

[0115]

[Table 7]

[0116]

As described above, the low crystalline ethylene random copolymer of the present invention has a narrow molecular weight distribution and a narrow composition distribution,
It has excellent transparency, non-stickiness on the surface, and low crystallinity.

The above copolymer of the present invention is incorporated into a thermoplastic resin to improve various properties of the resin.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 20, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Statement

Title: Low crystalline ethylene random copolymer

[Claims]

[Outside 1] (D) The crystallinity determined by X-ray diffraction is 30% or less, and (e) the following formula (I):

(Equation 1) [In the formula, P _E represents the content mole fraction of the ethylene component in the copolymer, P _o represents the content mole fraction of the α-olefin component, and P _oE is the α-olefin / ethylene chain of all dyad chains. The B value represented by the formula [II] 1.05 ≦ B ≦ 2 (II) is within the range, and (f) ¹³ C-NMR spectrum shows No signals of αβ and βγ based on a methylene chain between two adjacent tertiary carbon atoms in the combined backbone are observed, and (g) the boiling methyl acetate soluble part is 2% by weight or less,
A low-crystalline ethylene-based random copolymer characterized by the above.

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a low crystalline ethylene random copolymer. More specifically, it relates to a low-crystalline ethylene-based random copolymer having a narrow molecular weight distribution and a narrow compositional distribution, excellent transparency, surface non-adhesiveness and mechanical properties.

[0002]

2. Description of the Related Art Conventionally, low crystallinity ethylene / α-olefin copolymers have been in increasing demand for soft molding applications and various resin modifiers. As a production method thereof, a method is known in which ethylene and α-olefin are copolymerized in the presence of a titanium catalyst composed of a titanium compound and an organoaluminum compound or a vanadium catalyst composed of a vanadium compound and an organoaluminum compound. The low crystalline ethylene / α-olefin copolymer obtained with a titanium-based catalyst generally has a wide molecular weight distribution and composition distribution, and is inferior in transparency, surface non-adhesiveness and mechanical properties. In addition, the low crystalline ethylene / α-olefin copolymer obtained with the vanadium catalyst has a narrower molecular weight distribution and composition distribution than those obtained with the titanium catalyst, and it has transparency, surface non-adhesiveness and mechanical properties. However, they are still insufficient for applications requiring these performances, and there is a need for low crystalline ethylene / α-olefin copolymers with improved performance.

On the other hand, a catalyst comprising a zirconium compound and aluminoxane has recently been proposed as a new Ziegler type olefin polymerization catalyst.

In JP-A-58-19309, the following formula (cyclopentadienyl) ₂ Me R Hal, wherein R is cyclopentadienyl, C ₁ -C ₆ -alkyl, halogen and Me is A transition metal, Hal
Is a halogen, and a transition metal-containing compound represented by the following formula: Al ₂ OR ₄ (Al (R) -O) _n, wherein R is methyl or ethyl, and n is a number of 4 to 20, In the presence of a linear aluminoxane represented by the following formula (Al (R) -O) _{n + 2,} wherein R and n are the same as defined above, and a cyclic aluminoxane represented by the following formula, ethylene and C ₃ -C 1 species of ₁₂ α- olefin or 2
A method for polymerizing one or more species at a temperature of -50 ° C to 200 ° C is described. The publication describes that in order to control the density of the polyethylene obtained, the polymerization of ethylene should be carried out in the presence of small amounts of up to 10% by weight of somewhat longer-chain α-olefins or mixtures. .

Japanese Patent Laid-Open No. 59-95292 discloses the following.
formula

[0006]

Embedded image

Here, n is 2 to 40 and R is C ₁ to
A linear aluminoxane represented by the following formula, which is C ₆ -alkyl, and the following formula:

[0008]

Embedded image

[0009] Here, the definition of n and R is the same as described above, and an invention relating to a method for producing a cyclic aluminoxane represented by is described. For example, when methylaluminoxane and a bis (cyclopentadienyl) compound of titanium or zirconium are mixed and olefin polymerization is carried out, 25 g or more of polyethylene can be obtained per 1 g of transition metal and per hour. Have been described.

Japanese Unexamined Patent Publication No. 60-35005 discloses the following formula

[0011]

Embedded image

Wherein R ¹ is C ₁ -C ₁₀ -alkyl and R ⁰ is R ¹ or is bonded to represent --O-- and the aluminoxane compound of the formula is first reacted with a magnesium compound, The reaction product is then chlorinated,
Further, a method of producing a polymerization catalyst for olefin by treating with a compound of Ti, V, Zr or Cr is disclosed.
The publication describes that the catalyst is particularly suitable for the copolymerization of a mixture of ethylene and C ₃ -C ₁₂ α-olefin.

Japanese Unexamined Patent Publication No. 60-35006 discloses a catalyst system for producing a reactor blend polymer, which comprises mono-, di- or tri-cyclopentadienyl of two or more different transition metals or a derivative thereof (a). And alumoxane (aluminoxane) (b) are disclosed. In Example 1 of the publication, ethylene and propylene are polymerized using bis (pentamethylcyclopentadienyl) zirconium dimethyl and alumoxane as catalysts to give a number average molecular weight of 15,300, a weight average molecular weight of 36,400 and a propylene component. It is disclosed that a polyethylene containing 3.4% was obtained. In Example 2, ethylene and propylene were polymerized with bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride and alumoxane as catalysts, and the number average molecular weight was 2,200.
Toluene-soluble portion containing propylene component of weight average molecular weight 11,900 and 30 mol% and number average molecular weight 300
0, polyethylene having a weight average molecular weight of 7,400 and a propylene component having a number average molecular weight of 2,000, a weight average molecular weight of 8,300 and 7.1 mol% consisting of a toluene insoluble portion containing a propylene component having a weight average molecular weight of 7,400 and 4.8 mol%. ethylene·
A blend of propylene copolymer is obtained. Likewise

[0014]

[Outside 2]

Mol% soluble part and molecular weight distribution 3.04
And a blend of LLDPE and an ethylene-propylene copolymer consisting of an insoluble part of propylene component 2.9 mol%.

JP-A-60-35007 discloses that ethylene alone or with α-olefin having 3 or more carbon atoms and metatheron and the following formula (R-Al-O) n, wherein R has 1 to 5 carbon atoms. Is an alkyl group, and n is 1
Is to about 20 integer, in cyclic alumoxane or the following formula _{R (R-Al-O)} n AlR 2 where expressed, definitions of R and n are as defined above, in the linear alumoxanes represented A method of polymerizing in the presence of a catalyst system containing is described. According to the description of the publication, the polymer obtained by the method has a weight average molecular weight of about 500 to about 1.4 million and a molecular weight distribution of 1.5 to 4.0.

Further, in JP-A-60-35008, by using the least catalyst system comprising two meta Rose down and alumoxane, polyethylene or ethylene and _C 3 _{-C 10} having a width broader molecular weight distribution Α-olefin copolymers of

[0018]

[Outside 3]

It has been described that

Further, Japanese Patent Application Laid-Open No. 60-35009 discloses a vanadium compound and an organic aluminum.

[0021]

[Outside 4]

Disclosed is a method for producing a copolymer of ethylene and α-olefin which is less than or equal to less.

[0023]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel low crystalline ethylene random copolymer.

[0024] Another object of the present invention has a narrow molecular weight distribution and composition distribution, and to provide transparency, surface non-tackiness and dynamical was excellent in and low-crystalline ethylene random copolymer.

Still another object of the present invention is to provide a low crystalline ethylene-based random copolymer which, when blended with a thermoplastic resin, gives a composition excellent in impact resistance, particularly low temperature impact resistance.

Still another object of the present invention is to provide a low crystalline random copolymer which, when blended with a thermoplastic resin, gives a composition having excellent heat sealability.

Still another object of the present invention is to provide a low crystalline random copolymer which gives a composition having excellent transparency when blended with a thermoplastic resin.

Still another object of the present invention is to provide use of the low crystalline ethylene random copolymer of the present invention as a compounding agent for thermoplastic resin.

Further objects and advantages of the present invention will be apparent from the following description.

[0030]

According to the present invention, the low crystallinity ethylene-based random copolymer from ethylene and α-olefin having 4 to 10 carbon atoms is used. (A) the content of the ethylene component is in the range of 35 to 85% by weight, and the content of the α-olefin component is in the range of 15 to 65% by weight, (b) in decalin at 135 ° C. Intrinsic viscosity [η] measured in the range of 0.5 to 10 dl / g,

[0031]

[Outside 5]

(D) The crystallinity determined by the X-ray diffraction method is 30% or less, and (e) the following formula (I):

[0033]

(Equation 2)

[Wherein P _E represents the mole fraction of the ethylene component contained in the copolymer, P _o represents the mole fraction of the α-olefin component contained, and P _OE represents the α-olephine of all dyad chains. The B value represented by [indicating the mole fraction of ethylene chain] is in the range satisfying the following formula (II) 1.05 ≦ B ≦ 2 (II), and (f) ¹³ C-NMR spectrum shows , No signals of αβ and βγ based on a methylene chain between two adjacent tertiary carbon atoms in the copolymer main chain are observed, and (g) the boiling methyl acetate soluble part is 2.0 wt% or less. A low crystallinity ethylene-based random copolymer characterized by:

The low crystalline ethylene random copolymer of the present invention is (A) a zirconium hydride compound having a group having a conjugated π electron as a ligand, and (B)
It can be produced by the process of the present invention in which ethylene is copolymerized with α-olefin having 4 to 10 carbon atoms in the presence of a catalyst comprising aluminoxane.

The zirconium hydride compound (A) having a ligand having a group having a conjugated π electron is, for example, the following formula (III) R ¹ R ² R ³ ZrH (III) where R ¹ is a cycloalkadienyl group. And R ² and R ³ are a cycloalkadienyl group, an aryl group, an alkyl group, a halogen atom or a hydrogen atom.

The cycloalkadienyl group is, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl group or a tetrahydroindenyl group. Examples of the alkyl group of R ² and R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Examples of the aryl group include
For example, a phenyl group, a benzyl group, a neofuryl group and the like can be exemplified, and the halogen atom can include fluorine, chlorine, bromine and the like. Examples of the zirconium hydride compound include the following compounds.

Bis (cyclopentadienyl) zirconium monochloride, bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methylzirconium hydride, bis (cyclopentadienyl) ethylzirconium hydride , Bis (cyclopentadienyl) cyclohexyl zirconium hydride, bis (cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (methyl Cyclopentadienyl) zirconium monochloride monohydride, bisindenyl zirconium monochloride monohydride, above The ruconium hydride compound can be used as it is, but a compound such as bis (cyclopentadienyl) zirconium monochloride monohydride which is poorly soluble in a solvent such as toluene is used after contacting with an organoaluminum compound. It is preferable. By this operation, the solvent-insoluble zirconium hydride compound can be made easily soluble in the solvent.

Specific examples of the organoaluminum compound to be brought into contact with the zirconium hydride compound include trialkylaluminums such as trimethylaluminum, triethylaluminum and tributylaluminum, trialkenylaluminums such as triisoprenylaluminum, dimethylaluminum methoxide and diethyl. In addition to dialkylaluminum alkoxides such as aluminum ethoxide and dibutylaluminum butoxide, alkylaluminum sesquialcosides such as methylaluminum sesquimethoxide and ethylaluminum sesquiethoxide, R ¹ _2.5 Al (OR ² ) _0.5 Partially alkoxylated alkylaluminum, dimethylaluminium chloride, die having the average composition represented Partial aluminum dichlorides such as aluminum chloride, dimethylaluminum bromide, alkylaluminum sesquichlorides such as methylaluminum sesquichloride, alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, alkylaluminum dihalides such as methylaluminum dichloride and ethylaluminum dichloride. Examples thereof include halogenated alkyl aluminum.

The reaction between the two compounds is preferably carried out in a hydrocarbon medium, with or without light, and the mixing molar ratio (Al / Zr) of the organoaluminum compound and the zirconium compound is 0.
5 to 30, preferably 1 to 20, and the zirconium concentration is 0.001 to 1 mol, preferably 0.1.
005-0.1 mol, and the reaction temperature is 0-120.
The temperature may be set to about ° C and both may be brought into contact. The hydrocarbon medium can be selected from those exemplified as the solvent for polymerization described later.

Specific examples of the aluminoxane (B) as a catalyst constituent used in the method of the present invention include general formula (IV) or general formula (V).

[0042]

Embedded image

(In the formula, R represents a hydrocarbon group, m is preferably an integer of 20 or more, and particularly preferably an integer of 25 or more). In the aluminoxane, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group, and m is preferably 20 or more. It represents an integer, particularly preferably an integer of 25 or more, particularly preferably an integer of 30 to 100. The following method can be exemplified as a method for producing the aluminoxane.

(1) Compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, etc. Method of adding and reacting.

(2) A method in which water is allowed to act directly on a trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

Of these methods, the method (1) is preferably adopted. The aluminoxane may contain a small amount of an organic metal component.

In the above method, the raw material supplied to the polymerization reaction system is a mixture of ethylene and α-olefin having 4 to 10 carbon atoms other than ethylene. The content of ethylene in the polymerization raw material olefin is usually 10 to 90 mol%, preferably 20 to 80 mol%, and the content of the α-olefin is usually 10 to 90 mol%, preferably 20 to 80 mol%. It is a range.

As the α-olefin having 4 to 10 carbon atoms other than ethylene used as a raw material for polymerization in the above method, specifically , 1 -butene, 1-hexene, 4-methyl-1-pentene, 1-octene. , etc. 1-de-Ce emissions can be exemplified.

In the above method, the olefin polymerization reaction is usually carried out in a hydrocarbon medium. Specific examples of the hydrocarbon medium include butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane,
Aliphatic hydrocarbons such as octadecane, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane and other alicyclic hydrocarbons, benzene, toluene,
In addition to aromatic hydrocarbons such as xylene, petroleum fractions such as gasoline, kerosene, and light oil, olefin as a raw material also serves as a hydrocarbon medium. Of these hydrocarbon media, aromatic hydrocarbons are preferred.

In the above method, a liquid phase polymerization method such as a suspension polymerization method or a solution polymerization method is usually adopted, and a solution polymerization method is particularly preferably adopted. The temperature during the polymerization reaction is -50 to 200 ° C, preferably -30 to 100.
C., particularly preferably in the range of -20 to 80.degree.

The ratio of the zirconium hydride compound (A) used when the above method is carried out by the liquid phase polymerization method is
The concentration of zirconium metal atoms in the polymerization reaction system is usually in the range of 10 ⁻⁸ to 10 ⁻² gram atom / l, preferably 10 ⁻⁷ to 10 ⁻³ gram atom / l.
The aluminoxane content is usually 10 ⁻⁴ to 1 as the concentration of aluminum atoms in the polymerization reaction system.
0 ⁻¹ gram atom / l, preferably 10 ⁻³ to 5 ×
It is in the range of 10 ⁻² gram atom / l, and the ratio of aluminum metal atom to zirconium metal atom in the polymerization reaction system is usually 25 to 10 ⁷ , preferably 10
It is in the range of ² to 10 ⁶ . The molecular weight of the copolymer can be adjusted by hydrogen and / or the polymerization temperature.

In the above method, the low crystallinity ethylene copolymer of the present invention can be obtained by treating the polymerization reaction mixture after completion of the polymerization reaction by a conventional method.

The composition of the low crystalline ethylene copolymer of the present invention has an ethylene component of 35 to 85% by weight, preferably 40 to 80% by weight, and the α-olefin component of 15 to 65% by weight, preferably 20 to 50% by weight. It is in the range of 60% by weight.

The low crystalline ethylene random copolymer of the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.5 to 10 dl / g), preferably 1 to 6 dl / g. Has a value in the range of g.

The molecular weight distribution (Mw / Mn) of the low crystalline ethylene copolymer measured by gel permeation chromatography (GPC) is 2.5 or less,
The range is preferably 2.3 or less, particularly preferably 2 or less. When the molecular weight distribution of the low crystalline ethylene copolymer is larger than 2.5, the copolymer or the composition containing the copolymer as a modifier becomes too sticky or becomes blocked. Therefore, it is necessary to be within the above range.

The low crystalline ethylene copolymer has a low crystallinity and its crystallinity determined by X-ray diffraction is 30.
% Or less, preferably 20% or less, particularly preferably 0 to 15%.

[0057]

[Outside 6]

According to "Romatographie", the procedure is as follows.

(1) Using standard polystyrene having a known molecular weight (Toyo Soda (manufactured by Toyo Soda) monodisperse polystyrene),
Molecular weight M and its GPC (Gel Permeation)
Chromatograph) count is measured and a correlation diagram calibration curve of molecular weight M and EV (Elution Volume) is prepared. The concentration at this time is 0.02% by weight.

(2) GPC chromatograph of the sample is taken by GPC measurement, and by the above (1)

[0061]

[Outside 7]

Find the value. The sample preparation conditions and GPC measurement conditions at that time are as follows.

[Sample preparation] (a) A sample is placed in an Erlenmeyer flask together with an o -dichlorobenzene solvent so as to be 0.1% by weight.

(B) The antioxidant, 2,6-di-tert-butyl-p-cresol, is added to the Erlenmeyer flask containing the sample in an amount of 0.05% by weight based on the polymer solution.

(C) The Erlenmeyer flask is heated to 140 ° C. and stirred for about 30 minutes to dissolve it.

(D) The filtrate is applied to GPC.

[GPC measurement conditions] The measurement was carried out under the following conditions.

(A) Apparatus Waters (150C-
ALC / GPC) (b) Column Toyo Soda (GMH type) (c) Sample amount 400 μl (d) Temperature 140 ° C. (e) Flow rate 1 ml / min Furthermore, the low crystalline ethylene copolymer of the present invention is as follows: Formula (I)

[0069]

(Equation 3)

[Wherein P _E represents the mole fraction of the ethylene component contained in the copolymer, P _o represents the mole fraction of the α-olefin component contained, and P _OE represents the α-olephine of the entire dyad chain. The B value represented by [indicates the mole fraction of ethylene chain] is in a range that satisfies the following formula (II) 1.05 ≦ B ≦ 2 (II).

The above-mentioned B value is an index showing the distribution state of each monomer component in the copolymer chain. J. Ray
(Macromolecules, 10 , 773 (19
77)); C. Randall (Macromol
ecules, 15 , 353 (1982), J. Am. Pol
ymer Science, Polymer Phys
ics Ed. , 11 , 275 (1973)), K.S. K
imura (Polymer, 25 , 441 (198
4)) It is calculated by _obtaining P _E , P _o and P _oE defined above based on the report of et al. The larger the above B value, the less the block-like chain, the ethylene and α
-The copolymer has a uniform distribution of olefin and a narrow composition distribution.

The low crystalline ethylene copolymer of the present invention comprises:
It preferably has the following B value.

When the ethylene content of the copolymer is 50 mol% or less: 1.0 + 0.3 × P _E ≦ B ≦ 1 / (1-P _E ), more preferably the general formula 1.0 + 0.4 × P _E ≦ B ≦ 1 / (1-P _E ), particularly preferably the general formula 1.0 + 0.5 × P _E ≦ B ≦ 1 / (1-P _E ), when the ethylene content of the copolymer is 50 mol% or more. : 1.3-0.3 × P _E ≦ B ≦ 1 / P _E , more preferably the general formula 1.4-0.4 × P _E ≦ B ≦ 1 / P _E , particularly preferably the general formula 1.5. −0.5 × P _E ≦ B ≦ 1 / P _E , the composition distribution B value is about 20 in a sample tube of 10 mmφ.
A ¹³ C-NMR spectrum of a sample in which 0 mg of the copolymer was uniformly dissolved in 1 ml of hexachlorobutadiene was measured at a measurement temperature of 120 ° C. and a measurement frequency of 25.05M.
Hz, spectrum width 1500 Hz, filter width 150
0 Hz, pulse repetition time 4.2 sec, pulse width 7
The measurement was performed under the measurement conditions of μsec and the number of integration of 2000 to 5000 times, and from this spectrum, P _E , P. , _PoE was calculated. Furthermore, in the ¹³ C-NMR spectrum of the low crystalline ethylene copolymer of the present invention, αβ and βγ signals based on a methylene chain between two adjacent tertiary carbon atoms in the copolymer main chain are shown. Is not observed. For example, in a copolymer of ethylene and 1-hexene, the following bond:

[0074]

Embedded image

When viewed from the tertiary carbon on the left side derived from 1-hexene, the three central methylene groups are α from the left side,
It is located at β and γ positions, while it is located at α, β, and γ positions from the right when viewed from the tertiary carbon on the right side. Therefore, there is a methylene group giving the signals of αγ and ββ in the above binding unit, but no methylene group giving the signals of αβ and βγ.

Similarly, 1-hexene comrades bound head to tail were:

[0077]

Embedded image

In FIG. 5, there is only a methylene group that gives an αα signal, and there is no methylene group that gives an αβ and βγ signals.

On the other hand, the following bond

[0080]

Embedded image

Each has a methylene group that provides a βγ signal and an αβ signal, respectively. From the above description, it is clear that the low crystalline ethylene-based copolymer of the present invention has a regular bonding direction of a monomer copolymerizable with ethylene.

The boiling crystalline methyl acetate soluble content of the low crystalline ethylene random copolymer of the present invention is 2% by weight or less, preferably 1.5 to 0.01% by weight, particularly preferably 1.0.
-0.03% by weight, particularly preferably 0.7-0.0%
It is in the range of 5% by weight. When the weight fraction P _EW of the ethylene component unit of the low crystalline ethylene random copolymer is set, the boiling methyl acetate soluble amount [E _x wt%] of the low crystalline ethylene random copolymer is preferably is preferably from E _x ≦ 2.2-2 × _{P EW} particularly preferably E _x ≦ _{1.35-P EW} in the range of E _x ≦ 0.9-0.6 × _{P EW.}

For the measurement of the amount of boiling methyl acetate extracted, 1 sample was used.
After making a press sheet with a thickness of mm, this press sheet was cut into 2 mm × 2 mm square pieces and put in a cylindrical glass filter, and the reflux frequency was set to about 1/5 minutes, and the soxhlet extractor was performed for 6 hours. . The extraction amount was determined by drying the rest of the extraction with a vacuum dryer until a constant weight was obtained.

The low crystalline ethylene random copolymer of the present invention usually has a density of 0.90 g / cc or less. The stress at break and the elongation at break are 300 kg each.
/ Cm ² or less and 400% or more. The density was measured after the sample was heat-treated at 120 ° C. for 1 hour and gradually cooled to room temperature over 1 hour. The stress at break and the elongation at break are ring-shaped test pieces (inner diameter 18 mm, outer diameter 22 mm, thickness 1 m
m) was prepared and measured at a tensile speed of 500 mm / min and a measurement temperature of 25 ° C.

The low crystalline ethylene random copolymer of the present invention has a narrower molecular weight distribution and composition distribution as compared with the copolymer obtained by using a titanium catalyst, and has transparency, surface non-adhesiveness and It can be said that it has excellent mechanical properties. Further, it can be said that the molecular weight distribution and the composition distribution are almost the same or narrower than that of the copolymer obtained by using the vanadium-based catalyst, but the arrangement state of the copolymerization component in the molecular chain is different.

The low crystalline ethylene random copolymer of the present invention can be blended with various thermoplastic resins as a modifier thereof.

By blending the low crystalline ethylene random copolymer of the present invention with another ethylene polymer containing ethylene as a main component, such as polyethylene, the impact resistance of the other ethylene polymer is improved, particularly at low temperature. An ethylene polymer composition having improved impact resistance, bending resistance, and low temperature heat sill resistance is obtained, and the ethylene polymer composition has a transparency and a surface by blending a low crystalline ethylene random copolymer. It is characterized in that it does not reduce non-stickiness. Examples of the other ethylene-based polymers include high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1 −
Dodecene, 1-tetradecene, 1-hexadecene, 1-
Examples thereof include copolymers with α-olefin having 3 to 20 carbon atoms such as octadecene and 1-eicosene, and ethylene-based copolymers containing ethylene as a main component. The intrinsic viscosity [η] measured in decalin at 135 ° C. is usually in the range of 0.5 to 20 dl / g.

When the low crystalline ethylene random copolymer of the present invention is blended with the other ethylene polymer, the blending ratio is usually 0.5 to 100 parts by weight of the other ethylene polymer. It is in the range of 30 parts by weight, preferably 1 to 20 parts by weight. The resulting ethylene-based polymer composition, if necessary, an antioxidant, a hydrochloric acid absorbent, an anticoagulant, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather resistance stabilizer, an antistatic agent, a nucleating agent, a pigment, Various additives such as a filler can also be blended. The mixing ratio is appropriate. The ethylene polymer composition can be prepared according to a conventionally known method.

Further, the low crystalline ethylene random copolymer of the present invention is blended with a crystalline olefin polymer other than the other ethylene polymers to obtain a molded product of the crystalline olefin polymer. The impact resistance, especially at low temperature, and the addition of the low crystalline ethylene random copolymer does not bring about a decrease in transparency and surface non-adhesiveness. Specific examples of the crystalline olefin polymer other than the ethylene polymer include polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-1-hexene, and propylene ethylene. Copolymer, propylene / 1-butene copolymer, 1-
Α-olefin (a ₁ ) such as propylene, 1-butene, 1-hexene and ethylene, propylene, 1-butene, 1-hexene, such as butene / ethylene copolymer and 1-butene / propylene copolymer. , 4-methyl-1-
Pentene, 1-octene, 1-decene, 1-dodecene,
1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like, α-olefin having 2 to 20 carbon atoms, which is different from α-olefin (a ₁ ) and α-olefin (a ₂ ). Crystalline α-
An olefin-based copolymer can be exemplified. The intrinsic viscosity [η] of the crystalline olefin polymer measured in decalin at 135 ° C. is usually 0.5 to 10 dl / g.
And the crystallinity is 5% or more, preferably 20% or more.

When the low crystalline ethylene random copolymer of the present invention is blended with the crystalline α-olefin polymer, the blending ratio is 100% of the crystalline α-olefin polymer.
It is usually in the range of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight with respect to parts by weight. The crystalline α-olefin polymer composition may optionally contain an antioxidant,
Hydrochloric acid absorber, anti-agglomeration agent, heat stabilizer, UV absorber,
Various additives such as a lubricant, a weather resistance stabilizer, an antistatic agent, a nucleating agent, a pigment and a filler can also be added. The crystalline α-
The olefin polymer composition can be prepared according to a conventionally known method.

Furthermore, the low crystalline ethylene random copolymer of the present invention can be incorporated into various engineering resins to improve the physical properties of the engineering resins, such as impact resistance and sliding characteristics. In addition, the blending of the low crystalline ethylene random copolymer is characterized in that the transparency and the surface non-tackiness are not lowered. When the engineering resin is an engineering resin having a polar group, in order to improve the affinity or dispersibility to the engineering resin, the low crystalline ethylene random copolymer of the present invention, maleic acid, Modified ethylene-based random copolymers obtained by graft-copolymerizing unsaturated carboxylic acids such as citraconic acid, itaconic acid, maleic anhydride, citraconic acid anhydride, itaconic anhydride, dimethyl maleate, dimethyl citraconate, and dimethyl itaconic acid derivatives. Preference is given to using coalescence. The graft ratio of the unsaturated dicarboxylic acid or its derivative component is usually in the range of 0.02 to 50 parts by weight with respect to 100 parts by weight of the low crystalline ethylene random copolymer. Specifically as the engineering resin, polyethylene terephthalate, polyester such as polybutylene terephthalate, hexamethylene adipamide, octamethylene adipamide, decamethylene adipamide, dodecamethylene adipamide, polycaprolactone,
Polyamide such as, polyarylene oxide such as polyphenylene oliside, polyacetal, ABS, AE
S, polycarbonate and the like can be exemplified. The blending ratio of the low crystalline ethylene random copolymer or its modified product is usually in the range of 0.2 to 20 parts by weight with respect to 100 parts by weight of the engineering resin. The engineering resin composition may contain an antioxidant,
Hydrochloric acid absorber, anti-agglomeration agent, heat stabilizer, UV absorber,
Various additives such as lubricants, weather resistance stabilizers, antistatic agents, nucleating agents, pigments and fillers can be added. The engineering resin composition can also be prepared according to a conventionally known method.

The low crystalline ethylene random copolymer of the present invention can be mixed with various rubber-like polymers to improve the physical properties of the rubber-like polymer, such as chemical resistance and rigidity. Specifically as the rubber-like polymer,
Examples thereof include ethylene / propylene / non-conjugated diene copolymer, ethylene / 1-butene / non-conjugated diene copolymer, polybutadiene rubber, polyisoprene rubber, and styrene / butadiene / styrene block copolymer. The blending ratio of the low crystalline ethylene random copolymer is usually in the range of 1 to 100 parts by weight based on 100 parts by weight of the rubber-like polymer. If necessary, various fillers such as a filler, a cross-linking agent, a cross-linking aid, a pigment and a stabilizer can be added to the rubber-like polymer composition. The rubbery polymer composition can be prepared according to a conventionally known method.

[0093]

EXAMPLES The following describes the present onset bright examples specifically.

Example 1 Preparation of Zirconium Catalyst A 100 ml glass flask thoroughly purged with nitrogen was charged with 30 ml of toluene and 2 mmol of bis (cyclopentadienyl) zirconium monochloride monohydride to form a slurry. 20 mmol of trimethylaluminum (1M solution) diluted with toluene was added dropwise thereto at room temperature. After the dropping was completed, the temperature was raised to 60 ° C. and the reaction was performed for 1 hour. Bis (cyclopentadienyl) zirconium monochloride monohydride was dissolved in toluene and the solution became dark red. The above reaction was carried out by cutting off light.

Preparation of Methylaminooxane In a 400 ml glass flask sufficiently purged with argon, 13.9 g of magnesium chloride hexahydrate and 125 ml of toluene were charged, and after cooling to 0 ° C., 125 m of toluene was added.
250 mmol of trimethylaluminum diluted with 1 was added dropwise. After dropping, the temperature was raised to 70 ° C.
The reaction was performed for 6 hours. After the reaction, solid-liquid separation was performed by filtration, and toluene was removed from the separated liquid under reduced pressure to obtain 7.3 g of white solid methylaluminoxane. The molecular weight determined by freezing point depression in benzene is 1910.
And the m-value of the aluminoxane was 31.
During the polymerization, the aluminoxane was redissolved in toluene before use.

Polymerization Using a continuous polymerization reactor of 2 liters, purified toluene was 2 liters / hr, methylaluminoxane was 10 mg atom / hr in terms of aluminum atom, and the zirconium catalyst prepared above was 1 liter in terms of zirconium atom. × 1
It was continuously fed at a rate of 0 ^-2 milligram atoms / hr,
360 liters / h of ethylene simultaneously in the polymerization vessel
Polymerization was carried out under the conditions of a polymerization temperature of 20 ° C., an atmospheric pressure, a residence time of 0.5 hours, and a polymer concentration of 36 g / liter, by continuously supplying at a rate of r of 1-butene of 240 liters / hr. The produced polymer solution was continuously withdrawn from the polymerization vessel, the polymerization was stopped by adding a small amount of methanol, the polymer solution was transferred into a large amount of methanol, and the precipitated polymer was dried under reduced pressure at 130 ° C. for 12 hours. .

[0097]

[Outside 8]

Crystallinity 2.1%, B value 1.14, density 0.
A rubber-like polymer having 888 g / cm ³ and a boiling methyl acetate extraction amount of 0.31% by weight was obtained. The stress at break and the elongation at break of this polymer were 110 kg / cm ² and 9 respectively.
00%. ¹³ C-NM of this polymer obtained
No signals based on αβ and βγ were observed in the R spectrum. The activity per unit zirconium is 7300
g-polymer / milligram atom-Zr.

[0099] The procedure of Example 1 was repeated except that the polymerization was conducted under the conditions shown in Table 1. In the ¹³ C-NMR spectrum of the obtained polymer, no signals based on αβ and βγ were observed. The results are shown in Table 1.

Comparative Example 2 Tetrabutoxy titanium 2 was placed in an 800 ml SUS pot containing 2.8 kg SUS balls (15 mmφ).
g and 20 g of anhydrous magnesium chloride were put therein, and the mixture was ground for 8 hours in a nitrogen atmosphere (vibration mill). The co-ground product was transferred into 200 ml of ethylene dichloride and heated at 80 ° C. for 2 hours. Thereafter, the co-ground product was filtered off and washed with n-decane until no free titanium tetrachloride was detected. 21 g of titanium atoms were supported on 1 g of the catalyst thus obtained.

Polymerization Using the same polymerization reactor as used in Example 1, purified decane was 2 liters / hr, ethylaluminum sesquichloride was 8 mg atom / hr in terms of aluminum atom, and the titanium catalyst prepared above was converted to titanium atom in terms of titanium atom. It is continuously fed at a rate of 0.4 mg atom / hr, and is continuously fed at a rate of 300 liter / hr of ethylene and 100 liter / butene of 100 liter / hr at the same time in the polymerization system. Polymerization was carried out under the conditions of pressure, residence time of 0.5 hours and polymer concentration of 50 g / liter. The subsequent operation was performed according to Example 1. No signals based on αβ and βγ were observed in the ¹³ C-NMR spectrum of the obtained polymer. Table 2 shows the results.

Comparative Example 3 Using the same polymerization reactor as in Example 1, 2 parts of purified hexane was used.
L / hr Ethyl aluminum sesquichloride was continuously supplied at a rate of 1 mg atom / hr in terms of aluminum atom, and vanadyl trichloride was 0.1 mg atom / hr in terms of vanadium atom, and 200 liters of ethylene were simultaneously fed in the polymerization vessel. / Hr, propylene 240 liters / hr at a rate of continuous feeding, polymerization temperature 50
Polymerization was carried out under conditions of a temperature of 0 ° C., atmospheric pressure, a residence time of 0.5 hours, and a polymer concentration of 4 g / liter. The subsequent operations were exactly the same as in Example 1. ¹³ C of the obtained polymer
-In the NMR spectrum, unlike Examples 1 to 8, αβ,
A signal based on βγ was observed. Table 3 shows the results.

Comparative Examples 4 to 6 The same procedure as in Comparative Example 3 was carried out except that the polymerization was conducted under the conditions shown in Table 3. In the ¹³ C-NMR spectrum of the obtained polymer, signals based on αβ and βγ were observed as in Comparative Example 3. Table 3 shows the results.

[0104] Ethylene random copolymers and polyethylene resins (MFR 0.44 g / 10 min,
A density of 0.959 g / cm ³ ) was melt-mixed at a ratio of 1: 9, and then a press film having a thickness of 70 μ was prepared (1
80 ° C, 5 minutes preheat → degassing 30 seconds → 30 kg / cm ²
Pressurization, hold for 4 minutes 30 seconds → cold press at 20 ℃, 50k
g / cm ² pressurization for 3 minutes). About this film 23
The film impact strength and the transparency (haze value) at C and -20 C were measured. Table 4 shows the results.

Application Example 6 Comparative Application Examples 7 to 9 Ethylene random copolymers of the above Examples and Comparative Examples and polypropylene resin (MFR 10 g / 10 min) were melt mixed at a ratio of 1: 9, and then pressed with a thickness of 30 μm. A film was prepared (similar to Application Example 1). The film impact strength and transparency (haze value) at 23 ° C. of this film were measured. Table 5 shows the results.

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

[Table 6]

[0112]

[Table 7]

[0113]

As described above, the low crystalline ethylene random copolymer of the present invention has a narrow molecular weight distribution and a narrow composition distribution,
It has excellent transparency, non-stickiness on the surface, and low crystallinity.

The above copolymer of the present invention is incorporated into a thermoplastic resin to improve various properties of the resin.

[Brief description of the drawings]

FIG. 1 is a flow chart showing a manufacturing process of a copolymer according to the present invention.
It is a chart.

[Procedure amendment 2]

[Document name to be amended] Drawing

[Correction target item name] Fig. 1

[Correction method] Added

[Correction contents]

FIG.

Claims (1)

[Claims] 1. Ethylene and α having 4 to 10 carbon atoms
A low crystalline ethylene random copolymer from olefin, wherein: (a) the content of ethylene component is in the range of 35-85% by weight, and the content of α-olefin component is 15-.
65% by weight, and (b) the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 10 dl / g. (D) The crystallinity determined by X-ray diffractometry is 30% or less, and (e) the following formula (I): [In the formula, P _E represents the content mole fraction of the ethylene component in the copolymer, P _O represents the content mole fraction of the α-olefin component, and P _OE represents the α-olefin / ethylene chain of the entire dyad chain. B) represented by the following formula (II) 1.05 ≦ B ≦ 2 (II), and (f) ¹³ C-NMR spectrum shows No signals of αβ and βγ based on a methylene chain between two adjacent tertiary carbon atoms in the combined main chain are observed, and (g) the boiling methyl acetate soluble part is 2% by weight or less,
A low-crystalline ethylene-based random copolymer characterized by the above.