JPH06820B2 - Low crystalline ethylene random copolymer and its use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a low crystalline ethylene random copolymer and its use. More specifically, it relates to a low crystalline ethylene random copolymer having a narrow molecular weight distribution and a narrow compositional distribution, excellent transparency, surface non-adhesiveness and mechanical properties, and uses thereof.

[Conventional technology]

Conventionally, the demand for low crystalline ethylene / α-olefin copolymers has been expanding more and more for applications such as soft molding and various resin modifiers. As its manufacturing method,
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,
Moreover, the transparency, surface non-adhesiveness and mechanical properties were poor. In addition, the low crystalline ethylene / α-olefin copolymer obtained with a vanadium catalyst has a narrower molecular weight distribution and composition distribution than that obtained with a titanium catalyst, and has transparency, surface non-adhesiveness, and mechanical properties. However, they are not sufficient for applications requiring these performances, and there is a need for low crystalline ethylene / α-olefin copolymers having 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.

JP 58-19309 A discloses the following formula (cyclopentadienyl) ₂ Me R Hal, where R is cyclopentadienyl, C ₁ -C ₆ -alkyl, halogen, and Me is a transition metal. And Hal is 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 from 4 to 20. In the presence of a linear aluminoxane represented by: or a formula (Al (R) -O) _{n + 2,} wherein R and n have the same definitions as above, and a cyclic aluminoxax represented by , Ethylene, and one or more of C _{3 to} C ₁₂ α-olefins are polymerized at a temperature of −50 ° C. to 200 ° C. 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. .

JP-A-59-95292 discloses the following formula. Here, n is 2 to 40, R is C _{1 to} C ₆ alkyl, and a linear aluminoxane represented by: Here, the definitions of n and R are the same as above, and the 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 Patent Application Laid-Open No. Sho 60-35005 discloses the following formula Where R ¹ is C ₁ -C ₁₀ alkyl and R ⁰ is R
^The aluminoxane compound represented by the formula ¹ or bonded to represent -O- is first reacted with a magnesium compound, and then the reaction product is chlorinated, and Ti, V, Zr is further added.
Alternatively, a method for producing a polymerization catalyst for olefin by treating with a compound of 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 Patent Application Laid-Open No. 60-35006 discloses a catalyst system for producing a reactor blend polymer, wherein mono-, di- or tri-cyclopentanedienyl of two or more different transition metals or its derivative (a) and an alkyl sun are used. (Aluminoxane)
The combination of (b) is 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 15,30.
It is disclosed that a polyethylene containing 0, a weight average molecular weight of 36,400 and a propylene component of 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 of A number-average molecular weight of 2,000 comprising a toluene-soluble portion containing a propylene component having an average molecular weight of 11,900 and 30 mol% and a toluene-insoluble portion containing a number-average molecular weight of 3000 and a weight-average molecular weight of 7,400 and 4.8 mol%. A blend of polyethylene and an ethylene / propylene copolymer containing a propylene component having a weight average molecular weight of 8,300 and 7.1 mol% is obtained. Similarly, in Example 3, the molecular weight distribution (w / n) of 4.57 and the soluble portion of the propylene component 20.6 mol% and the molecular weight distribution of 3.04 and the propylene component 2.
LLDPE consisting of 9 mol% insoluble part and ethylene-
Blends of propylene copolymers are described.

JP-A-60-35007 discloses that ethylene alone or together with α-olefin having 3 or more carbon atoms and metallocene and the following formula (R-Al-O) _n, wherein R is an alkyl group having 1 to 5 carbon atoms. Yes, 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 is about 500 to about 1.
It has a weight average molecular weight of 400,000 and a molecular weight distribution of 1.5 to 4.0.

Further, in JP-A-60-35008, by using a catalyst system containing at least two kinds of metallocene and alumoxane, polyethylene having a broad molecular weight distribution or a mixture of ethylene and C ₃ -C ₁₀ α-olefins is used. It is described that a polymer is produced. The publication describes that the copolymer has a molecular weight distribution (w / n) of 2 to 50.

Further, JP-A-60-35009 discloses a copolymer of ethylene and α-olefin which has a small molecular weight distribution (w / n) of less than 2 by using a catalyst system containing a vanadium compound and an organoaluminum compound. A method of manufacturing is disclosed.

[Problems to be solved by the invention]

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

Another object of the invention is to have a narrow molecular weight distribution and composition distribution,
It is intended to provide an ethylene-based random copolymer which is excellent in transparency, surface non-adhesiveness and mechanical properties and has 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 excellent in 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 a use of the low crystalline ethylene random copolymer of the present invention as a compounding agent for a thermoplastic resin.

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

[Means and Actions for Solving Problems]

Such an object and advantage of the present invention are, according to the present invention, a low crystalline ethylene-based random copolymer from ethylene and α-olefin having 4 to 10 carbon atoms, wherein (a) the content of the ethylene component is: Is in the range of 35 to 85% by weight, and the content of the α-olefin component is 15 to 6
In the range of 5% by weight, (b) the intrinsic viscosity [η] measured in decalin at 135 ° C.
Is in the range of 0.5 to 10 dl / g, (c) the molecular weight distribution (w / n) determined by gel permeation chromatography is 2.5 or less, and (d) crystallization determined by X-ray diffraction method. The degree is 30% or less, (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 _{Po E} is the α-olefin / ethylene chain of the entire dyad chain. The B value represented by the following formula (II) is in a range satisfying the following formula (II) 1.05 ≦ B ≦ 2 (II), and (f) in the ¹³ C-NMR spectrum, The αβ and βγ signals based on the methylene chain between two adjacent tertiary carbon atoms in the chain are not observed, and (g) the boiling methyl acetate soluble part is 2.1% by weight or less. Achieved by a low crystalline ethylene random copolymer.

The low crystallinity ethine series 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) in the presence of a catalyst comprising aluminoxane, ethylene. And the number of carbon atoms is 4 to 1
It can be prepared by the method of the present invention in which 0 α-olefin is copolymerized.

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

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

Bis (cyclopentadienyl) zirconium monochloride, bis (cyclopentadienyl) zirconium monopromide 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 (methylcyclopenta) (Dienyl) zirconium monotalolide monohydride, bisindenyl zirconium monochloride monohalide, the above-mentioned zirconium Although the mu-hydride compound can be used as it is, a compound that is poorly soluble in a solvent such as toluene such as bis (cyclopentadienyl) zirconium monochloride monohydride should be used after contacting with an organoaluminum compound. Is preferred. 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 contacted with the zirconium hydride compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, and tributylaluminum, trialkenylaluminums such as triisoprenylaluminum, dimethylaluminum methoxide, and diethylaluminum ethoxide. In addition to dialkylaluminum alkoxides such as dibutyl aluminum butoxide, alkylaluminum sesquimethoxide such as methylaluminum sesquimethoxide and ethylaluminum sesquiethoxide, a partial composition having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 Alkoxy aluminum, dimethyl aluminum chloride, diethyl aluminum chloride Lido, dialkyl aluminum halides such as dimethyl aluminum bromide, alkyl aluminum sesquichlorides such as methyl aluminum sesquichloride, alkyl aluminum sesquichlorides such as ethyl aluminum sesquichloride, alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, etc. 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 Is 0 per liquid phase.
001 to 1 mol, preferably about 0.005 to 0.1 mol, and the reaction temperature may be set to about 0 to 120 ° C. to bring them into contact with each other. The hydrocarbon medium can be selected from those exemplified as the solvent for polymerization described later.

Specifically as the aluminoxane (B) of the catalyst constituent used in the method of the present invention, the general formula (IV) or general formula
(V) (In the formula, R represents a hydrocarbon group, m preferably represents 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) A compound containing adsorbed water, a salt containing water of crystallization, for example, trialkylaluminum is added to a hydrocarbon medium suspension such as magnesium chloride hydrate, copper sulfate hydrate, and aluminum sulfate hydrate. To react.

(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 (1)
It is preferable to adopt the method of. The aluminoxane may contain a small amount of 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 8 mol%.
In the range of 0 mol%, as the α-olefin having 4 to 10 carbon atoms other than ethylene used as a polymerization raw material in the above method, specifically, 1-butene, 1-hexene, 4-methyl-1- Pentene, 1-octene, 1-decene, etc. can be illustrated.

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, octadecane, and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane, and other alicyclic groups. In addition to hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and 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 in the range of -50 to 200 ° C, preferably -30 to 100 ° C, particularly preferably -20 to 80 ° C.

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

In the above-mentioned 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 is 85% by weight without ethylene component, preferably 40 to 80.
% By weight, the α-olefin component is in the range of 15 to 65% by weight, preferably 20 to 60% by weight.

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

The molecular weight distribution (Mw / Mn) of the low crystalline ethylene copolymer measured by gel permeation chromatography (GPC) is 2.5 or less, preferably 2.3 or less,
The range of 2 or less is particularly preferable. When the molecular weight distribution of the low crystalline ethylene copolymer becomes larger than 2.5,
It is necessary that the content of the copolymer or the composition containing the copolymer as a modifier increases in stickiness or causes blocking, so that the content is within the above range.

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

The w / n value is measured according to "Gel Permeation Chromatography" by Takeuchi, Maruzen.

(1) Correlation between molecular weight M and EV (Elution Volume) by measuring molecular weight M and its GPC (Gel Permeation Chro-matograph) count using standard polystyrene of known molecular weight (Toyo Soda (manufactured by Toyo Soda)) Create a calibration curve. The concentration at this time is 0.02 wt%.

(2) A GPC chromatograph of the sample is taken by GPC measurement, and the polystyrene-reduced number average molecular weight n and weight average molecular weight w are calculated according to the above (1) to obtain the w / n value. The sample preparation conditions and GPC measurement conditions in that case are as follows.

[Sample preparation]

(B) The sample is dispensed into an Erlenmeyer flask together with the O-dichlorobenzene solvent so that the concentration of the sample becomes 0.1 wt%.

(B) Anti-aging agent 2, in the Erlenmeyer flask containing the sample
6-di-tert-butyl-P-cresol is added at 0.05 wt% with respect to the polymer solution.

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

(D) Pour the liquid on GPC.

[GPC measurement conditions]

 It carried out on the following conditions.

(A) Equipment Waters (150C-ALC / GPC) (b) Column Toyo Soda (GMH type) (c) Sample amount 400μ (d) Temperature 140 ° C (e) Flow rate 1 ml / min Furthermore, low of the present invention The crystalline ethylene-based copolymer has the following formula (I) [In the formula, P _E represents the content mole fraction of the ethylene component in the copolymer, Po represents the content mole fraction of the α-olefin component, and Po _E represents the α-olefin / ethylene chain of the entire dyad chain. B value represented by the following formula] is in a range satisfying the following formula (II) 1.05 ≦ B ≦ 2 (II).

The above B value is an index showing the distribution state of each monomer component in the copolymer chain, and GJRay (Macromolecules,
10 , 773 (1977)), JCRandall (Macromole
cules, 15 , 353 (1982), J. Polymer Scienc
e, Polymer Physics Ed. , 11 , 275 (197)
3)), K. Kimura (Polymer, 25 , 441 (198)
4)) Based on the above report, P _E , Po and Po
It is calculated by finding _E. The larger the B value, the smaller the number of blocky chains, and the more uniform the distribution of ethylene and α-olefin, indicating that the copolymer has a narrow composition distribution.

The low crystalline ethylene copolymer of the present invention 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 200 in a 10 mmφ sample tube.
The ¹³ C-NMR spectrum of a sample obtained by uniformly dissolving mg of the copolymer in 1 ml of hexachlorobutadiene was
Measurement temperature 120 ° C, measurement frequency 25.05MHz, spectrum width 1500Hz, filter width 1500Hz, pulse repetition time 4.2sec, pulse width 7μsec, integration count 2000
From this spectrum, measured under ~ 5000 times of measurement conditions
It was calculated by calculating P _E , Po, and Po _E. 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, the following bond: Is the central three methylene groups at the positions α, β, γ from the left when viewed from the tertiary carbon on the left derived from 1-hexene, while α, β from the right when viewed from the tertiary carbon on the right. ,
It is in the γ position. Therefore, although there are methylene groups in the above binding units that give the signals of αγ and ββ, αβ
There are no methylene groups that give the signals of βγ.

Similarly 1-hexene comrades bound head-to-tail with the following bonds: Exists only in methylene groups that give αα signals, and there is no methylene group that gives αβ and βγ signals.

On the other hand, the following combination and Each have a methylene group that provides a βγ signal and an αβ signal.

As is clear from the above description, it is understood that the low crystalline ethylene-based copolymer of the present invention has a regular bonding direction of a monomer copolymerizable with ethylene.

The low crystalline ethylene random copolymer of the present invention has a boiling methyl acetate soluble content of 2% by weight or less, preferably 1.5 to 0.0.
It is in the range of 1% by weight, particularly preferably 1.0 to 0.03% by weight, particularly preferably 0.7 to 0.05% by weight. When the weight fraction of the ethylene component unit of the low crystalline ethylene random copolymer is P _E w, the boiling methyl acetate soluble content of the low crystalline ethylene random copolymer [Ex wt%]
Is preferably Ex ≦ 2.2−2 × P _E w, more preferably Ex ≦ 1.35−P _E w, and particularly preferably Ex ≦ 0.9−0.6 × P _E w.

To measure the amount of boiling methyl acetate extracted, make a 1 mm thick press sheet from the sample, then shred this press sheet into 2 mm x 2 mm squares and put it in a cylindrical glass filter. Reflux frequency is about 1/5 minutes. I went to the Soxhlet extractor 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 is usually 0.
It has a density of 90 g / cc or less. The stress at break and the elongation at break are 300 kg / cm ² or less and 400% or more, respectively. 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 (internal diameter 18 mm,
Outer diameter 22mm, thickness 1mm), and pulling speed 500mm
/ Min, the measurement temperature was 25 ° C.

The low crystalline ethylene random copolymer of the present invention has a narrow molecular weight distribution and composition distribution and is transparent, has a non-tacky surface and has mechanical properties as compared with the copolymer obtained using a titanium catalyst. It can be said that it is excellent. 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 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 low temperature impact resistance An ethylene-based polymer composition having improved flex resistance and low-temperature heat sill resistance is obtained, and the ethylene-based polymer composition has a transparency and a surface non-adhesiveness due to the incorporation of a low crystalline ethylene-based random copolymer. The feature is that it does not cause a decrease in Examples of the other ethylene-based polymer include high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-
Penten, 1-octene, 1-decene, 1-dodecene,
Examples include 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like, which are copolymers with α-olefin having 3 to 20 carbon atoms and which contain ethylene as a main component. can do. 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 30 parts by weight, preferably 100 parts by weight of the other ethylene polymer. Is in the range of 1 to 20 parts by weight. The resulting ethylene-based polymer composition, if necessary, an antioxidant, a hydrochloric acid absorbent, an agglomeration inhibitor, a heat stabilizer,
UV absorber, lubricant, weather resistance stabilizer, antistatic agent, nucleating agent,
Various additives such as pigments and fillers can also be blended. The mixing ratio is appropriate. The ethylene polymer composition can be prepared according to a conventionally known method.

Further, by blending the low crystalline ethylene random copolymer of the present invention with a crystalline olefin polymer other than the other ethylene polymer, the impact resistance of a molded article made of the crystalline olefin polymer is improved. Properties, especially at low temperature, and by blending the low crystalline ethylene random copolymer, transparency and surface non-tackiness are not lowered. 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. Α-such as propylene, 1-butene, 1-hexene, such as a copolymer, a propylene / 1-butene copolymer, a 1-butene / ethylene copolymer, and a 1-butene / propylene copolymer.
Olefin (a ₁ ) and ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, Crystalline α-olefin copolymers such as 1-eicosene and the like having 2 to 20 carbon atoms and α-olefin (a ₂ ) different from α-olefin (a ₁ ). Can be illustrated. The intrinsic viscosity [η] of the crystalline olefin polymer measured in decalin at 135 ° C. is usually in the range of 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 usually 0.5 to 100 parts by weight of the crystalline α-olefin polymer. It is in the range of 30 parts by weight, preferably 1 to 20 parts by weight. The crystalline α-olefin polymer composition may optionally contain an antioxidant, a hydrochloric acid absorbent,
Various additives such as an anti-aggregation agent, a heat resistance stabilizer, an ultraviolet absorber, a lubricant, a weather resistance stabilizer, an antistatic agent, a nucleating agent, a pigment and a filler can also be blended. The crystalline α-olefin polymer composition can be prepared by a conventionally known method.

Furthermore, by blending the low crystalline ethylene random copolymer of the present invention into various engineering resins,
A feature that the physical properties of the engineering resin, such as impact resistance and sliding properties, can be improved, and that the incorporation of the low crystalline ethylene random copolymer does not cause a decrease in transparency and surface non-adhesiveness. There is. 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. Specific examples of the engineering resin include polyesters such as polyethylene terephthalate and polybutylene terephthalate, hexamethylene adipamide, octamethylene adipamide, decamethylene adipamide, dodecamethylene adipamide, and polyamides such as polycaprolactone.
Examples thereof include polyarylene oxide such as polyphenylene oxide, polyacetal, ABS, AES, and polycarbonate. 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 include an antioxidant, a hydrochloric acid absorbent, an anticoagulant, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather stabilizer, an antistatic agent, a nucleating agent, a pigment, a filler, etc., if necessary. Various additives can be blended. The engineering resin composition can also be prepared according to a conventionally known method.

By blending the low crystalline ethylene random copolymer of the present invention with various rubber-like polymers, physical properties of the rubber-like polymer, such as chemical resistance and rigidity, can be improved. Specific examples of the rubber-like polymer include ethylene / propylene / non-conjugated diene copolymer, ethylene /
Examples thereof include 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.

〔Example〕

 Next, 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 mono- (lidomonohydride was dissolved in toluene to give a dark red solution. The above reaction was carried out with or without light.

Preparation of Methylaminooxane In a 400 ml glass flask sufficiently purged with argon, 13.9 g of 6 aqueous solution of magnesium chloride and 12 parts of toluene were added.
After charging 5 ml and cooling to 0 ° C., 250 mmol of trimethylaluminum diluted with 125 ml of toluene was added dropwise. After the dropping was completed, the temperature was raised to 70 ° C. and the reaction was performed at that temperature for 96 hours. After the reaction, the individual liquid was separated by filtration, and toluene was further 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 was 1910, and the m value of the aluminoxane was 31. During the polymerization, the alumina oxane was redissolved in toluene before use.

Using a continuous polymerization reactor having a weight of 2,
hr, methylaluminoxane is continuously supplied at a rate of 10 mg atom / hr in terms of aluminum atom, and the gilconium catalyst prepared above is continuously supplied at a rate of 1 × 10 ^-2 mg atom / hr in terms of zirconium atom at the same time in the polymerization vessel. Ethylene was continuously fed at a rate of 360 / hr 1 butene 240 / 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 / hr.
The polymer solution produced is continuously withdrawn from the polymerization vessel,
Stop the polymerization by adding a small amount of methanol,
Further, 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. Ethylene content 77% by weight, [η] 2.16 dl / g, w / n
1.85, crystallinity 2.1%, B value 1.14, density 0.888 g / cm ³ ,
A rubbery polymer having a boiling methyl acetate extraction 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 900%, respectively. The ¹³ C-NMR spectrum of the obtained polymer was αβ,
No signal based on βγ was observed. The activity per unit zirconium was 7300 g-polymer / milligram atom-Zr.

Examples 2 to 9 and Comparative Example 1 Except that the polymerization was carried out under the conditions shown in Table 1, the same procedure as in Example 1 was carried out. No signal based on αβ or βγ was observed in the ¹³ C-NMR spectrum of the obtained polymer. The results are shown in Table 1.

Comparative Example 2 Preparation of Titanium Catalyst 800 m with 2.8 kg SUS ball (15 mmφ) built-in
2g of tetrabutoxytitanium and 20g of anhydrous magnesium chloride were placed in an SUS porato of 1 and placed under a nitrogen atmosphere.
Milled for hours (vibration mill). The co-crushed product was transferred into 200 ml of ethylene dichloride and heated at 80 ° C. for 2 hours. afterwards,
The co-ground product was 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, 2 parts of purified decane was used.
/ Hr, ethylene aluminum sesquichloride is 8 mg atom / hr in terms of aluminum atom, and the titanium catalyst prepared above is 0.4 mg atom / hr in terms of titanium atom.
At a rate of 300 / hr and 100 / hγ of 1-butene continuously at a rate of 300 / hr in the polymerization reactor system at a polymerization temperature of 120 ° C., atmospheric pressure and a residence time of 0.5 hours. Polymerization was carried out under the condition that the polymer concentration was 50 g /. After that, the necessary conditions were the same as in Example 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 2.

Comparative Example 3 Using the same polymerization reactor as in Example 1, 2 parts of purified hexane was used.
/ Hr Ethylaluminum sesquichloride is continuously supplied at a rate of 1 mg atom / hr in terms of aluminum atom, and vanadyl trichloride is 0.1 mg atom / hr in terms of vanadium atom, and ethylene 2 is simultaneously fed in the polymerization vessel.
Polymerization was carried out under the conditions of a polymerization temperature of 50 ° C., an atmospheric pressure, a residence time of _0.5 hours, and a polymer concentration of 4 g /, while continuously supplying 00 / hr propylene at 240 / hr. The subsequent operations were exactly the same as in Example 1. The ¹³ CNR spectrum of the obtained polymer was different from that of Examples 1 to 8 by α
Signals based on β and βγ were observed. The results are shown in Table 3.

Comparative Examples 4 to 6 The procedure of Comparative Example 3 was repeated 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. The results are shown in the third.

Application Examples 1 to 5, 7 Comparative Examples 1 to 6 Ethylene random copolymers and polyethylene resins (MFP 0.44 g / 10 min, density 0.5)
59 resin / cm ³ ) was melt-mixed at a ratio of 1: a, and a play film having a thickness of 70 μ was prepared (180 ° C., 5 minutes preheating → degassing 30 seconds → 30 kg / cm ² pressurization, 4 minutes 30 seconds. Hold → cold press at 20 ℃, pressurize 50kg / cm ^{2 for} 3 minutes). The film impact strength and transparency (haze value) at 23 ° C. and −20 ° C. were measured for this film. The results are shown in Table 4.

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 a press film having a thickness of 30 μ was prepared. (Same as application example 1). The film impact strength and transparency (haze value) at 23 ° C. were measured for this film. The results are shown in Table 5.

[Effect of the invention] As described above, the low crystalline ethylene random copolymer of the present invention has a narrow molecular weight distribution, a narrow composition distribution, and excellent transparency,
It is non-sticky on the surface and has 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 drawings]

FIG. 1 is a flow chart showing the steps for producing the copolymer according to the present invention.

Claims (2)

[Claims] 1. Ethylene and α-containing 4 to 10 carbon atoms.
A low crystalline ethylene random copolymer derived from olefin, wherein the content of (a) ethylene component is in the range of 35 to 85% by weight, and the content of α-olefin component is 15 to 6%.
In the range of 5% by weight, (b) the intrinsic viscosity [η] measured in decalin at 135 ° C.
Is in the range of 0.5 to 10 dl / g, (c) the molecular weight distribution (w / n) determined by gel permeation chromatography is 2.5 or less, and (d) determined by X-ray diffraction method. Crystallinity is 30% or less, (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 _{Po E} is the α-olefin-ethylene chain of the entire dyad chain. Of the copolymer main component is in the range satisfying the following formula (II) 1.05 ≦ B ≦ 2 (II), and (f) ¹³ C-NMR spectrum shows The αβ and βγ signals based on the methylene chain between two adjacent tertiary carbon atoms in the chain are not observed, and (g) the boiling methyl acetate-soluble portion is 2% by weight or less. Low crystalline ethylene random copolymer. 2. The content of (a) ethylene component is 35 to 85.
A in the range of wt% and having 4 to 10 carbon atoms
The content of the olefin component is in the range of 15 to 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, (c) the molecular weight distribution (w / n) determined by gel permeation chromatography is 2.5 or less, and (d) crystallization determined by X-ray diffraction method. The degree is 30% or less, (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 _{Po E} is the α-olefin-ethylene chain of the entire dyad chain. B value represented by the formula [II] 1.05 ≦ B ≦ 2 (II) is satisfied, 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) boiling methyl acetate soluble part is 2.0% by weight or less, ethylene and carbon A compounding agent for a thermoplastic resin, which comprises a low-crystalline ethylene-based random copolymer of α-olefin having 4 to 10 atoms.