JPS62121707A - Production of alpha-olefin random copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer which is narrow in both MW distribution and composition distribution and can give a molding such as a film excellent in transparency, blocking resistance, heat sealability, impact resistance, etc., by copolymerizing a 3C or higher alpha-olefin with ethylene in the presence of a specified catalyst. CONSTITUTION:A catalyst (C) is obtained by using a Group IVB transition metal compound in which the ligand is a multidentate compound formed by bonding at least tow groups selected from among (substituted) indenyl group and partially hydrogenated products thereof through an alkylene group [e.g., ethylenebis(indenyl)dimethylzirconium] and an aluminooxane (b) of formula I or II (wherein R is a hydrocarbon group and m>=2) as components. A 3C or higher alpha-olefin (A) is copolymerized with ethylene (B) at -80-80 deg.C and a pressure of normal pressure to 30kg/cm<2> or a subatmospheric pressure to obtain the title copolymer containing 30-99mol% component A and 70-1mol% component B and having an intrinsic viscosity of 0.5-6dl/g (in decalin at 135 deg.C), a m.p. of 30-140 deg.C (differential scanning calorimetry) and a boiling methyl acetate-soluble portion <=1wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a method for producing a Namekawa α-olefin random copolymer. More specifically, α-olefin random copolymers have a narrow molecular weight distribution and composition distribution, and have excellent transparency, surface non-adhesion, tensile properties, and other properties. Heat-sealability and impact resistance can be achieved by blending with thermoplastic resins such as α-olefin random copolymers and other olefin polymers, which are suitable for forming packaging films, sheets, and other melt-molded products. This invention relates to a method for producing a modifier for thermoplastic resins that is particularly effective in improving impact resistance at low temperatures.

[Conventional technology] Conventionally, the use of vinyl chloride resin has been advantageous in the field of molding applications for soft or semi-hard resins, but there are concerns about the generation of corrosive scum during waste incineration and the safety of residual monomers and plasticizers. Due to such concerns, it has become desirable to switch to olefin-based soft or semi-rigid resins. Therefore, the demand for α-olefin-based soft copolymers is increasingly expanding in the field of molding or as modifiers for various resins.

The α-olefin-based soft copolymer includes two or more α-olefin-based soft copolymers.
- Copolymers of olefins are generally known, and their production method involves using two or more of them in the presence of a titanium-based catalyst consisting of a titanium compound and an organoaluminium compound or a vanadium-based catalyst consisting of a vanadium compound and an organoaluminum compound. Methods of copolymerizing the above α-olefins are known. α-olefin-based soft copolymers obtained with titanium-based catalysts generally have poor random copolymerizability;
It has a wide molecular weight distribution and composition distribution, and is poor in transparency, surface non-adhesion, and mechanical properties. In addition, α-olefin soft copolymers obtained using vanadium catalysts generally have an ethylene content of 50 mol% or more, and they have improved randomness compared to copolymers obtained using titanium catalysts. Although the molecular weight distribution and composition distribution are narrowed and the transparency, surface non-adhesiveness, and mechanical properties are considerably improved, these performances are still insufficient for applications where these performances are strictly required, and these performances are generally not satisfactory. There is a need for improved soft alpha-olefin copolymers.

Recently, olefin resins that have been used in the field of molding applications of soft or semi-hard resins include:
There are olefin copolymers such as ethylene copolymers, propylene copolymers, and 1-butene copolymers. Among these olefin-based soft or semi-hard resins,
Regarding the soft 1-butene-based random copolymer consisting of 1-butene and propylene, the main component of which is 1-butene,
There are many suggestions. Among them U.S. Patent No. 3.278
．． No. 504, US Pat. No. 3.332.921, US Pat. No. 4.168.361, and British Patent No. 1.018.341 contain titanium trichloride and titanium tetrachloride. A 1-butene-based random copolymer produced using a system catalyst is disclosed. However, these 1-
What all butene-based random copolymers have in common is that they have a high content of low-molecular polymer components such as boiling methyl acetate solubles and acetone/n-decane mixed solvent (volume ratio 1/1) solubles. In addition, since the composition distribution and molecular weight distribution are wide, molded articles formed from these 1-butene-based random copolymers, particularly films and sheets, have high surface tackiness and significant blocking.

Furthermore, most of them have low randomness and poor transparency, making it impossible to obtain molded products with high commercial value.

The specification of US Pat. No. 3,278,504 includes 1-
Propylene with a butene content of 30 to 70 mol% 1
-Butene copolymers have been proposed. It is described that the 1-butene-based copolymer is produced using titanium tetrachloride or titanium trichloride, but the copolymer produced using such a catalyst system contains a boiling methyl acetate soluble content. The amount exceeds 2% by weight, and the content of acetone/n-decane mixed solvent (volume ratio 1/1) is high, and the surface tackiness is
It is a soft resin with poor transparency.

The above-mentioned US Pat. No. 3,332,921 and British Patent No. 1,084,953 also describe various 1-butene contents produced using titanium trichloride catalysts.
Butene-based copolymers have been proposed, but among these copolymers, 1-butene-based copolymers with a 1-butene content of 60 to 99 mol%
-Butene-based copolymers are disclosed in the above-mentioned U.S. Patent No. 3,278,50.
It has the same properties as the 1-butene copolymer proposed in Specification No. 4.

Further, according to the specification of British Patent No. 1.018.341, a transition metal halide such as titanium trichloride and a phosphoric acid derivative are used in combination to increase the 1-butene content from 25 to 90.
mol % copolymer is obtained. Among the copolymers specifically disclosed in this proposal, a 1-butene-based copolymer containing 50 to 90 mol% of 1-butene has an acetone soluble content of 1.5 mol%. Only the above are disclosed. According to studies by the present inventors, these copolymers have a boiling methyl acetate soluble content exceeding 2% by weight, and acetone/n-decane mixed solvent (volume ratio 1/1) soluble content. The content of the 1-butene-based copolymer exceeds 5×[η]-1.2% by weight, which means that only molded products with high surface tackiness and poor transparency can be obtained from the 1-butene-based copolymer. Understood.

Furthermore, the aforementioned US Pat. No. 4,168.361 discloses propylene/1-butene copolymers having a propylene content in the range of 40 to 90 mol%; Regarding copolymers with a 1-butene content of 50 to 60 mol %, according to the study conducted by the present inventors, the content of soluble components in aceto/n-decane mixed solvent is high, and A 1-butene copolymer has a high surface tackiness and can only yield a molded article with poor transparency.

On the other hand, a method for obtaining an amorphous random copolymer by polymerizing at high temperature using a titanium trichloride catalyst was disclosed in JP-A-50-38.
This is proposed in Publication No. 787.

According to studies conducted by the present inventors, this method contains a large amount of methyl acetate soluble content and has poor tensile properties, making it unusable for resin applications.

In addition, the present applicant has disclosed that in JP-A No. 54-85293, the composition distribution is narrow, the boiling methyl acetate soluble content is small,
We have proposed a 1-butene/propylene random copolymer mainly composed of 1-butene, which has low surface tackiness. However, the content of the low molecular layer component of the 1-butene/propylene copolymer provided by this proposal, especially the content of the low molecular weight polymer represented by the boiling methyl acetate content, and the molding made of the copolymer It is clear that the surface adhesion of the product is considerably improved compared to conventional products, but
Molecular weight distribution of butene-based random copolymer (My/in
) is 3.6, which is not narrow enough, and the low molecular weight polymer components in the copolymer, especially acetone
Decane mixed solvent (volume ratio 1/1) The content of low molecular weight polymer components expressed as soluble content is still high, and the 1-butene/propylene random copolymer is added to polypropylene resin to improve impact resistance. Molded products made from blended resin compositions, such as films, have drawbacks such as the tendency for surface tackiness to increase over time, and are still difficult to use in fields where high performance such as surface non-tackiness and transparency is required. It was hard to say that it was sufficient. Furthermore, according to this proposal,
Propylene random copolymers have low crystallinity and poor mechanical properties such as rigidity, and are still inadequate for applications in fields where these mechanical properties are highly required.

On the other hand, as a new Ziegler-type olefin polymerization catalyst different from the conventionally known titanium-based catalysts or vanadium-based catalysts, catalysts made of a zirconium compound and aluminoxane are disclosed in JP-A-58-19309 and JP-A-5.
9-952925, JP 60-35005, JP 60-35006, JP 60-35
Previous proposals have been made in Publication No. 007 and Japanese Unexamined Patent Publication No. 60-35009. These prior art documents also exemplify copolymers of two or more α-olefins, such as Example 7 of JP-A-58-19309 and JP-A-6
Examples 1 to 3 of Publication No. 0-35006, JP-A No. 6
Examples 10 and 11 of Publication No. 0-35007 disclose ethylene/α-olefin copolymers with an α-olefin content of 3 to 43 mol%, but these ethylene/α-olefin copolymers All copolymers have wide molecular weight and composition distributions, transparency,
Performance such as surface non-adhesion and mechanical properties, as well as performance as a modifier for thermoplastic resins, are often insufficient depending on the application field, and further improvement of these properties is required.
- There is a strong demand for olefin-based soft copolymers.

In addition, regarding soft low-crystalline propylene-based copolymers containing a propylene component by copolymerizing propylene and an α-olefin other than propylene, the present applicant has disclosed JP-A-52-19153 and JP-A-55 -118
909, JP 55-118910, JP 53-79984, JP 53-104686
No. 1, JP-A-54-85293, JP-A-Sho 60-
It has been proposed in Publication No. 38414, etc. These soft, low-crystalline propylene-based copolymers have a lower content of boiling methyl acetate solubles than conventionally known soft, low-crystalline propylene-based copolymers, and have superior surface non-adhesion and blocking properties. and transparency are improved, but it is difficult to say that this is sufficient for applications in fields where these performances are more strictly required, and furthermore, the copolymers obtained by these methods all have poor intermolecular distribution. Broadly speaking, there is a strong demand for soft, low-crystalline propylene-based copolymers that are broadly superior in the above-mentioned properties for applications in fields where performance is strictly required in terms of physical properties as well.

[Problems to be Solved by the Invention] The present inventors have discovered that conventional α-olefin random copolymers have a wide molecular weight distribution and composition distribution, a high content of low molecular weight polymers, and L'RI indicates that molded articles obtained from random copolymers are inferior in mechanical properties such as surface non-adhesiveness, transparency, and rigidity, and these are compared to conventional α-olefin random copolymers. Development research has been conducted with the aim of providing α-olefin random copolymers with improved physical properties.

As a result, the present inventors have developed an α-olefin random copolymer consisting of an α-olefin component having 3 or more carbon atoms and an ethylene component, and
We have discovered that there is an α-olefin random copolymer that has the characteristic values defined in ) and has not been described in any prior art literature, and we have successfully synthesized it.

In general, this new α-olefin random copolymer has a narrower molecular weight distribution and composition distribution than conventional α-olefin random copolymers, and has a low molecular weight polymer component and a Soluble content and acetone
The content of the low molecular weight polymer component expressed as both the soluble content in the n-decane mixed solvent (volume ratio 1/1) is low, and the molded product obtained from the α-olefin random copolymer has a non-porous surface. They discovered that it has particularly excellent mechanical properties such as adhesiveness, transparency, and rigidity.

Therefore, an object of the present invention is to provide a method for producing a novel α-olefin random copolymer comprising an α-olefin component having 3 or more carbon atoms and an ethylene component.

Furthermore, another object of the present invention is to improve heat sealability or impact resistance, particularly low-temperature impact resistance, by blending it into thermoplastic resins such as olefin polymers obtained by methods other than the method of the present invention. The object of the present invention is to provide a method for producing a modifier for thermoplastic resins that is excellent in terms of quality.

The above objects and numerous other objects and advantages of the present invention will become more apparent from the following description.

[Means and effects for solving the problems] According to the present invention, an α-olefin having 3 or more carbon atoms and ethylene are selected from the group consisting of (A) an indenyl group, a substituted indenyl group, and a partially hydrogenated product thereof; A transition metal compound of group IVB of the periodic table having as a ligand a polydentate compound in which at least two selected groups are bonded via a lower alkyl group, and (B) an aluminoxane. A method for producing an α-olefin random copolymer, which comprises copolymerizing in the presence of a catalyst to obtain a copolymer having a content of 30 to 99 mol% of the α-olefin component, and the α-olefin random copolymer. A method for producing a thermoplastic resin modifier comprising an olefin random copolymer is provided.

By the above production method, an α-olefin random copolymer consisting of an α-olefin having 3 or more carbon atoms and ethylene, the composition of which is an α-olefin component having 3 or more rA atoms. is 30 to 99 mol% and the ethylene component is 1
1 to 70 mol% in (B) decalin.
Intrinsic viscosity [η] measured at 35°C is 0.5 to 5d
(C) Molecular weight distribution (M
W/VJn) is in the range of 3 or less, and (D) melting point [Tm] measured by differential scanning calorimeter.
(E) The degree of crystallinity measured by X-ray diffraction is in the range of 0°5 to 60%, (F) The amount of soluble matter in boiling methyl acetate [W > weight %] is in the range of 1% by weight or less, and (G) the amount of soluble matter in acetone/0-decane mixed solvent (capacity 1/1) at 10°C [W2 weight %1 is 4×[
η]-1. αβ and βγ signals based on methylene chains between two adjacent tertiary carbon atoms in the copolymer main chain in the L 3 C-NMR spectrum of the (H) copolymer; was not observed, (1) General formula [i] O5 B3□ [11 2P-P.

[In the formula, P represents the molar fraction of the α-olefin component contained in the copolymer, O5 represents the molar fraction of the ethylene component, and Po'F= represents the molar fraction of the α-olefin ethylene component in all dyad chains. An α-olefin random copolymer characterized in that the B value represented by 1 indicating the mole fraction of the chain is in the range of the general formula [II] 1.00≦B≦2 [■1] Thermal BJ made of α-olefin random copolymer
A modifier for plastic resin is obtained.

In the α-olefin random copolymer obtained by the method of the present invention (also referred to as the α-olefin random copolymer of the present invention), the composition (A) of the copolymer has an ethylene component of 1 to 70 mol %, preferably in the range of 1 to 65 mol %, and the hS content of the α-olefin component
$30 to 99 mol%, preferably 35 to 99 mol%
in the range of mol%. In addition, when the copolymer is a copolymer of propylene and ethylene, the content of ethylene is in the range of 10 to 70 mol%, preferably 20 to 65 mol%, and the content of ethylene is in the range of 10 to 70 mol%, preferably 20 to 65 mol%. In the case of a copolymer, the ethylene content is 1 to 50 mol%.
, preferably in the range of 1 to 40 mol. When the content of the α-olefin component in the copolymer becomes less than 30 mol% and the content of the ethylene component exceeds 70 mol%, the transparency of the copolymer decreases. Furthermore, if the content of the α-olefin component is greater than 99 mol% and the content of ethylene component is less than 1 mol%, the transparency and impact resistance will decrease and the characteristics of the soft copolymer will disappear. In addition, when the α-olefin component is a 1-butene component, the transition of the copolymer from ■-type crystals to T-type crystals is delayed, and the physical properties of the molded product change with time and the transparency decreases. It also becomes inferior. Here, the α-olefin component unit is an α-olefin having 3 to 20 carbon atoms, preferably an α-olefin having 3 to 18 carbon atoms, particularly preferably an α-olefin having 3 to 12 carbon atoms, and these 1+! ! 1 or a mixture of two or more components.

Specifically, such α-olefin component units are:
Examples include propylene, 1-butene, 1-pentene, 1-'\xene, 4-methyl-1-pentene, 1-hebutene, 1-octene, 1-decene, 1-tetradecene, 1-oftadecene, etc. be able to.

In the α-olefin random copolymerization obtained by the method of the present invention, the intrinsic viscosity [η1 (B) measured in decalin at 135°C is in the range of 0.5 to 6 dl/g, preferably K to 5 dl/g. It is in.

This characteristic value is a measure of the molecular weight of the α-olefin random copolymer produced by the method of the present invention, and together with other characteristic values, it gives the above-mentioned properties to the random copolymer. It is useful for

Gelvermiecimine chromatography (GPC) of α-olefin random copolymer obtained by the method of the present invention
The molecular weight distribution (MW /Mn ) (C) determined by is in the range of 3 or less, preferably 2.8 or less, particularly preferably 2.5 or less. Since the α-olefin random copolymers that have been proposed so far have a MW/Mn value of 3 or more, the molecular weight distribution cannot be said to be sufficiently narrow, and low-molecular monopolymer acid content is mixed. Therefore, the surface has poor non-adhesive properties,
This is causing blocking. This characteristic value in the α-olefin random copolymer obtained by the method of the present invention, together with other characteristic values, gives the copolymer the above-mentioned excellent properties. The Mwain value was measured as follows according to "Gel Permeation Chromatography" written by Takeuchi and published by Maruzen.

(1) Using standard polystyrene of known molecular weight (monodisperse polystyrene manufactured by Toyo Soda Co., Ltd.), molecule MM and its G
P C (G el P ern + ation C
hrom-atograph) counts and molecule IM and EV (E 1tion V o+u+me
) A correlation diagram calibration curve was created. The concentration at this time is 0.
02wt%.

(2) A GPC chromatograph of the sample was taken by GPC measurement, and the number average molecule IMn and i1m average molecule IMw in terms of polystyrene were extracted according to the above (1) to determine the Mw/Mn value. The sample preparation conditions and GPC measurement conditions at that time are as follows.

[Sample Preparation] (a) A sample was fractionated into an Erlenmeyer flask together with 0-dichlorobenzene solvent so that the concentration was 0.1 wt%.

(b) Add anti-aging agent to the Erlenmeyer flask containing the sample.
0.05 wt% of 6-tert-butyl p-cresol was added to the polymer solution.

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

(d) The r liquid was subjected to GPC.

[GPC measurement conditions] It was conducted under the following conditions.

(a) Equipment Manufactured by Waters (150C-ALC/
GPC) (b) Column Toyo Soda W (GMH type) (
c) Lean pull amount 400 μm (d) 1 degree 140°C (e) Flow rate 1 ml/min The melting point measured by a differential scanning calorimeter of the α-olefin random copolymer obtained by the method of the present invention [hereinafter referred to as D
Sometimes abbreviated as SC melting point] (D) is in the range of 30 to 140°C, preferably 40 to 120°C. The existence of this DSC melting point indicates that the conventional amorphous α-
It is a measure that indicates that the copolymer has crystallinity that is distinguishable from olefin-based random copolymers, and together with other characteristic values, it helps to give the copolymer the above-mentioned excellent properties. I'm here. Here, the DSC melting point is the sample 5m
(In the case of a 1-butene-based random copolymer, press sheet 1 was used after at least 20 hours after molding) was placed in a measurement sample case and heated at a heating rate of 10°C/1n for 20 to 200 minutes. It is the temperature (Tm) of the maximum endothermic peak obtained by measuring up to ℃.

The degree of crystallinity (E) measured by X-ray diffraction of the α-olefin random copolymer obtained by the method of the present invention is 0.
．． It ranges from 5 to 60%, preferably from 0.5 to 55%. This property value is a measure showing that the α-olefin random copolymer obtained by the method of the present invention has excellent tensile properties, and together with other property values, the above-mentioned excellent properties can be obtained from the random copolymer. It is helping to give.

The degree of crystallinity of the 1-butene-based random copolymer was determined by X-ray diffraction measurement of a pressed sheet 20 hours after molding.

In the α-olefin random copolymer obtained by the method of the present invention, the amount soluble in methyl manate [W 1% by weight] (F) is 1% by weight or more based on the weight of the copolymer. , preferably from 0.001 to 0.5% by weight, particularly preferably from 0.003 to 0.2% by weight. This characteristic value indicates the content of the low molecular weight polymer component in the α-olefin random copolymer obtained by the method of the present invention, and is a measure of the breadth and narrowness of the composition distribution and molecular weight distribution of the copolymer. The proposed α-olefin random copolymer has a large amount of boiling methyl acetate soluble content, which causes poor surface non-adhesion and high blocking property. This property value in the α-olefin random copolymer obtained by the method of the present invention, together with other property values, serves to provide the copolymer with the above-mentioned excellent properties. The boiling methyl acetate soluble content was measured by the following method. That is, 1111m x 1 mm x l
A strip sample of about mm in size was placed in a cylindrical glass filter, and extracted with a Soxhlet extractor for 7 hours at a reflux purity of about 15 minutes at a time.
0 mmHa or less) to a constant weight, calculate the weight, and calculate the boiling methyl acetate soluble content from the weight difference with the original sample.
[Wll was determined as the percentage of the weight of the boiling methyl acetate soluble content to the width loss of the original sample.

In the α-olefin random copolymerization obtained by the method of the present invention, the amount of soluble content in acemine/n-decane mixed solvent (volume ratio 1/1) at 10°C [W1% by weight]
(G) is the weight 1. Based on T, 4×[
η]-1.2% by weight or less, preferably 0.05X[η]
-1.2 to 3.5×[η]-1.2% by weight, particularly preferably 0.1×[η]-1. It is in the range of i to 3×[η1-y] (here, [η] is the numerical value of the intrinsic viscosity of the copolymer, excluding the dimension).

This characteristic value indicates the content of the low molecular weight polymer component in the α-olefin random copolymer obtained by the method of the present invention, and is a measure of the composition distribution and molecular weight range of the copolymer. Conventionally known α-olefin random copolymers have a large content soluble in the acetone/n-decane mixed solvent, which causes poor surface non-adhesion and high blocking properties. This property value in the α-olefin random copolymer obtained by the method of the present invention, together with other property values, serves to provide the copolymer with the above-mentioned excellent properties. The amount of the copolymer soluble in the mixed solvent is determined by the following method. That is,
19 copolymer samples, 0.05 g of 2゜6-di-tert-butyl-4-methylphenol, and 50 ml of n-decane were placed in a 150 ml flask equipped with a stirring blade.
Dissolve on an oil bath at °C. After dissolving, let it cool naturally in a room for 30 minutes, then add 50ml of acetone for 30 seconds,
Cool on a 10°C water bath for 60 minutes. The solution containing the precipitated copolymer and low molecular weight polymer component was separated by filtration (using a glass filter), and the solution was heated at 150°C at 10 mmHq.
The sample copolymer was dried to a constant weight and its weight was measured, and the amount of the copolymer soluble in the mixed solvent was calculated and determined as a percentage of the weight of the sample copolymer.

In the above measurement method, stirring was performed continuously from the time of dissolution to immediately before filtration.

In the α-olefin random copolymer of the present invention,
Arrangement state of ethylene component and α-olefin component (H)
Regarding this, in the l' C-NMR spectrum of the copolymer, no αβ and βγ signals based on methylene chains between two adjacent tertiary carbon atoms in the main chain of the copolymer are observed.

To explain this in detail, in the copolymer of ethylene and α-olefin (CHi=CHR: R is an alkyl group), the following bond 2 α β γ RR is the left 3 derived from α-olefin. Viewed from the grade carbon, the three central methylene groups are located at α, β, and γ from the left, while from the right side, viewed from the tertiary PA rope on the fabric side, the three methylene groups are located at positions α, β, and γ.
Located at β and γ positions. Therefore, in the above bonding unit, αγ
Although there is a methylene group that gives a signal of ββ and α
There are no methylene groups giving the β and βγ signals.

On the other hand, in the following bond α in which α-olefins are bonded head-to-tail, there is only a methylene group that gives an αα signal, and there is no methylene group that gives αβ and βγ signals.

On the other hand, the bonds α β γ δ and α β have methylene groups giving the βγ signal and the αβ signal, respectively.

As is clear from the above explanation, the α-olefin random copolymer obtained by the method of the present invention has ethylene and α
- It can be seen that the bonding direction of olefins is regular.

This specification in the α-olefin random copolymer of the present invention indicates the arrangement state of the ethylene component and α-olefin component that constitute the copolymer, and together with other characteristic values, it has the above-mentioned excellent properties. It helps in imparting properties to the copolymer.

The α-olefin copolymer of the present invention has the following formula % formula % (
) In formula 1, P represents the molar fraction of the ethylene component in the copolymer, P represents the molar fraction of the α-olefin component, and Po8 represents the molar fraction of the α-olefin/ethylene chain in all dyad chains. The B value represented by the mole fraction] is in a range that satisfies the following formula (II): 1.00≦8≦2 (n). Roughly speaking, the B value of the α-olefinic urundum copolymer obtained by the method of the present invention preferably has a relationship similar to that shown in the manual in relation to the molar fraction (P) of the ethylene component in the copolymer. .

1.0+ if the ethylene content of the copolymer is 50 mol% or less
0.3xP-≦8≦1/(1-P-), b
Particularly preferably, when the general formula is 1.010, bxP-≦B≦1/(1-P-), and the ethylene content of the copolymer is 50 mol% or more. :1.3-0
．． 3xP≦B≦1/P, W
6 More preferably, the general formula %Formula % Particularly preferably, the range satisfies the general formula 1.5-0.5xP, ≦8≦1/P5.

In the α-olefin random copolymer obtained by the method of the present invention, the characteristic value consisting of the B value is an index representing the phase separation state of each monomer component in the copolymer chain, and the larger the B value, the more block This shows that it is a copolymer with few physical chains, uniform distribution of ethylene component and α-olefin component, excellent randomness, and narrow composition distribution. It is useful for providing copolymers with excellent properties such as.

B la is G, J, RaV (Macrom
olecules.

10.773 (1977)), J.C.Randal
l(Macromolecules, 15.353
(1982) et al.) containing IP, PO, and σPo6. P, ,
Po and P were determined from 13C-NMR spectrum Q of the copolymer sample. That is, the 13cNMR of a sample in which approximately 200m() of copolymer was uniformly dissolved in 1n+I hexachlorobutadiene in a 10nlfflφ sample tube.
The spectrum is normally measured at an altitude of 120°C, a constant frequency of 25.05MHz, and a spectral width of 1500H2.
Filter width 1500Hz, pulse repetition time 4.
2sec, pulse width 7μsec, number of accumulations 2000~
Measured under the measurement conditions 5000 times, calculated P, P, P from this spectrum and calculated 5 Q OE
- It was.

The α-olefin random copolymer obtained by the method of the present invention satisfies the characteristic values specified in (A> or 1) above. A more preferred α-olefin random copolymer obtained by the method of the present invention has at least one of the following characteristic values (J) to R) in addition to the specific values (A) to 1) above. be satisfied.

In the α-olefin random copolymer obtained by the method of the present invention, the stress at break (Jl) measured by the method of JJS K6301 is 3 to 1000 kg/C.
l112, preferably 5 to 800 kg/cm2
The 1 tili point elongation (K1) measured by JIS K6301 (7) method is 300% or more, preferably in the range of 500 to 1500%. In the present invention, the above-mentioned stress at break (Jl) and elongation at break (
The characteristic values of Kl) were measured according to the tensile test method of JIs K6301. In other words, the sample is JIS K6
A ring-shaped test piece with an inner diameter of 18 mm and an outer diameter of 22111111 was made from a 1 mm thick press sheet C-formed by 758, and the tensile speed was 50 in an atmosphere of 25°C.
Measure at 0 mm/min.

In addition, in the α-olefin random copolymer of the present invention, the thickness l when molded according to JIS K6758
Bayes (M) measured on a sheet of mm according to JIS K6714 is in the range of 30% or more, preferably 20% or less.

When the α-olefin random copolymer obtained by the method of the present invention is a 1-butene random copolymer obtained by copolymerization of a 1-7 tenene component and an ethylene component, (J2), ( At least one of the characteristic values K2) and (N) or Q) is satisfied. That is, the stress at yield point (N> measured by the method of JIS K7113 is in the range of '1 to 200 ka/c+n2, preferably 2 to 180 k (1/cm2), and the stress at break point measured by the method of JIS K7113 ( J2) is in the range of 3 to 1000 kg/am2, preferably C5'; within the range of

In the present invention, the above-mentioned yield point stress (N), breaking point stress (
The characteristic values of J warp and elongation at break (K2) are JIS K7
It was measured according to the tensile test method of No. 113. That is,
Sample 1mm thick molded according to JIS K6758
JI was extracted from the press sheet after 19 hours of molding.
Using a two-arculate test piece of S K7113, the measurement is performed 20 hours after the press sheet forming described above at a tensile rate of 50 mmg/min in an atmosphere of 25°C. If the yield point was not clearly determined, 20% elongation stress was taken as the yield point stress.

Further, when the α-olefin random copolymer obtained by the method of the present invention is a 1-butene-based lantam copolymer C obtained by copolymerization of 1-butene and ethylene,
JIS K674 of the 1-butene-based random copolymer
The torsional rigidity (0) measured by the method of 5 is, for example, 5 to 3000 k(]/'cm2, preferably 1
It ranges from 0 to 2000 kq/cm'. The method for measuring the torsional rigidity was as follows: A press sheet with a thickness of 1 mm formed according to JIS K6758 was stamped 9 days after the molding, and the length was 54 + nn +, the width was 635 mm).
10 days after molding the I-less sheet using the υ vessel-shaped test piece, 25
5 after machining with a torsion angle of 50 to 60 degrees in an atmosphere of ℃
Measured the value of seconds.

JIS K71 of the 1-butyne random copolymer
The Young's modulus (P) measured by the method of No. 13 is, for example, 10 to 5000 kg/cma, preferably 20 to 4000 kQ/cm! within the range of

In addition, the Young's modulus (P
) is preferably expressed by the general formula % in relation to the ethylene component content b mol %. The Young's modulus was measured as described above (J2).
, (K2) and (N>) were measured using the same tensile test method.

When the α-olefin random copolymer obtained by the method of the present invention is a 1-butene random copolymer obtained by copolymerizing 1-butene and ethylene, the 1-1 tenene random copolymer The polymer is characterized in that its physical properties change less over time because the crystal transition progresses more rapidly than in the homopolymer of 1-butene. On the contrary,
For example, a 1-1 ten homopolymer has three types of crystal forms.
■ type, ■ type, and ■ type), and it is known that mutual crystal transitions occur as temperature and time change, especially v! Because the transition from the metastable ■-type crystal form to the stable ■-type crystal form is slow at high temperatures, various difficulties arise when applying it to actual molded products, such as deformation of the molded product and changes in physical properties over time. There are drawbacks such as:

The standard deviation value σ(Q) of the α-olefin component content of the α-olefin random copolymer is, for example, 0.4a.
It is not more than mol %, preferably not more than 0.2 q mol % (in the formula, a represents the mol % content of the ethylene component in the α-olefin random copolymer). The standard deviation value σ is a measure showing the randomness of the α-olefin random copolymer, and is a measure of the randomness of the α-olefin random copolymer, and is a copolymer that roughly satisfies the characteristic value (Q) in addition to the characteristic value (A) or P). Coalescence shows better physical properties. The standard deviation value σ of the α-olefin random copolymer of the present invention was determined by the following formula based on the composition distribution of the copolymer. The composition distribution of the copolymer was measured using an extraction column fractionation method in which the extraction temperature was changed stepwise from O to 130°C in steps of 5°C using p-xylene solvent. For copolymer sample 10 (+), p-xylene 21 was used, and extraction between 4118 and 4118 was performed.

a= [f”0(T-x) 2f(x)d
x]! 4Here, 7 indicates the average weight ratio (mol%) of α-olefin in the copolymer, and X represents the α-olefin content (mol%).
mol%), f(x) is α-olefin content x (mol%
) is the differential weight fraction of the component.

In the present invention, when the α-olefin random copolymer obtained by the method is a propylene random copolymer obtained by copolymerization of propylene and ethylene, the [3 Microisotoughness (R) as seen from propylene chain J
is 0.8 or more, preferably 0.9 or more. The value of microisotoughness is determined by "three propylene chains" which are the smallest units of steric structure among the propylene chains in the copolymer chain of the propylene random copolymer of the present invention (with an ethylene unit between them). X of the total number of possible combinations of
．． In the case of 4 propylene consecutive units, 2.5 in the case of 5 propylene consecutive units, whereas in the case of 3), the above-mentioned "3 propylene chains" have (q) three types of arrangement, that is, mm
array (tactical array), m-r array and r-
The ratio of the number y (y/x) to the "three propylene chains" in the mm arrangement in the r arrangement is shown.

As mentioned above, in the present invention, the microisotoughness as seen in three propylene chains is determined by focusing on three propylene chains using the 13c nuclear magnetic resonance spectroscopy method, which is known per se. This is a quantitative determination of the fraction in which three propylene units are arranged in a tactical manner.

Products with this value smaller than 0.8, such as those produced using vanadium catalysts, are usually 0.6 or less, but
Such copolymers have a low softening point and low tensile strength, and are therefore undesirable.

The α-olefin random copolymer obtained by the method of the present invention may be copolymerized with a trace amount of other α-olefin components as long as the above-mentioned physical properties are not impaired.

The α-olefin-based syndam copolymer obtained by the method of the present invention has a lower molecular weight than conventionally known α-olefin/ethylene-based random copolymers in the entire range of α-olefin component content. It has the characteristics of a low content of combined components, excellent transparency, excellent surface non-adhesion, and excellent rigidity and other mechanical properties.

The new α-olefin random copolymer is made by combining a predetermined amount of an α-olefin having 3 or more carbon atoms with ethylene, (A> selected from the group consisting of an indenyl group, a substituted indenyl group, and a partially hydrogenated product thereof). A catalyst formed from a transition metal compound of group IV B of the periodic table having as a ligand a polydentate compound in which at least two groups are bonded via a lower alkyl group, and (B) an aluminoxane. It can be produced by copolymerizing in the presence of

Titanium, zirconium and hafnium may be mentioned as transition metals of group IV B of the periodic table. Among these, zirconium is preferred.

Examples of transition metal compounds that can be used in the process of the invention where the transition metal is zirconium are ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl) Methylzirconium monochloride, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)methylzirconium monopromide, ethylenedos(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(4,5) ,6゜7-tetrahydro-1
-indenyl)dimethylzirconium, ethylenebis(
4,5,6,7-titrahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,
6,7=tetrahydro-1-indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, 5-methyl-1-indenyl) zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebis(7-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methoxy-1-indenyl) Zirconium dichloride, ethylene bis(2,3-
dimethyl-1-indenyl) zirconium dichloride,
Mention may be made of ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride and ethylenebis(1,7-dime]-xy-1-indenyl)zirconium dichloride.

Examples of transition metal compounds that can be used in the present invention where the transition metal is titanium include ethylene bis(indenyl) titanium dichloride and ethylene his(4,5,6
, 7-Te1-lahydro-1-indenyl) titanium dichloride.

The present invention can be used where the transition metal is hafnium; examples of transition metal compounds include ethylene bis(indenyl) hafnium dichloride and ethylene bis(4).
, 5,6,7-tetrahydro-1-indenyl) hafnium dichloride.

Specifically, the aluminoxane (B) of the catalyst component used in the method of the present invention has the general formula Cl] or the general formula [11] R2A t-4-OA 1f-OA t R2[I 3
(In the formula, R represents a hydrocarbon group, and m represents an integer of 2 or more, preferably 20 or more, particularly preferably 25 or more)
Examples include organoaluminum compounds represented by: In the aluminoxane, R is a methyl group,
A hydrocarbon group such as an ethyl group, a globyl group, or a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, where m is an integer of 2 or more, preferably an integer of 20 or more, particularly preferably is an integer from 25 to 100. The following method can be exemplified as a method for producing the aluminoxane.

(1) Trialkylaluminium is added to a hydrocarbon medium layer suspension of compounds containing adsorbed water, salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, etc. How to make a reaction.

(21 A method in which water is directly applied to trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

Among these methods, it is preferable to adopt the fil method. Note that the aluminoxane may contain a small amount of organometallic component.

In the present invention, by producing a copolymer of α-olefin and ethylene in a specific ratio using the catalyst system as described above, it is possible to obtain a copolymer with properties never proposed before. This is what I found.

Although the copolymerization of α-olefin and ethylene can be carried out in either the liquid phase or the gas phase, it is particularly preferable to carry out the copolymerization in the liquid phase. When carried out in the liquid phase, it is usually carried out in a hydrocarbon medium. As the hydrocarbon medium, for example, aliphatic hydrogen hydride such as pentane, hexane, hegetane, octane, decane, cyclopentane, methylcyclopentane,
Examples include alicyclic hydrocarbons such as cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene and xylene, and petroleum fractions such as gasoline, kerosene and light oil. In addition to these, the raw material olefin itself can also be used as the hydrocarbon medium. Among these hydrocarbon media, aromatic hydrocarbons are preferred.

When carrying out the method of the present invention by a liquid phase polymerization method, the proportion of the transition metal compound used is usually 10''7 to 10'''' gram atom/l as the concentration of transition metal atoms in the polymerization reaction system. , preferably from 10-6 to 10-s gram atom/
The range is 1. The proportion of aluminoxane to be used is usually 10-4 to 10-' 7t, preferably 10'' to 5 x 10-!, depending on the aluminum atoms in the polymerization reaction system. The amount should be within the range of Durham atoms/II, and the ratio of aluminum atoms to transition metal atoms in the polymerization reaction system is usually 20 to 10.
6, preferably in the range of 50 to 10'.

The copolymerization of the present invention can be carried out in the same manner as the polymerization of olefins using a conventional Cheedler type catalyst.

The copolymerization temperature is usually -80 to -50, preferably -
It is best to choose between 60 and 30. Furthermore, the polymerization can be carried out under normal pressure, increased pressure or reduced pressure, but it is preferable to carry out under increased pressure. Usually normal pressure or 31] kl? /4 preferably 2 to 20 kg/cd
This is done under moderate pressure.

The raw material supplied to the polymerization reaction system is preferably a mixture of α-olefin and ethylene. The content of α-olefin in the polymerization raw material olefin is usually 40 to 999 mol%, preferably 50 to 99.8 mol%.
, the content of ethylene is usually 0.1 to 60 mol%,
Preferably it is in the range of 0.2 to 50 mol%. The molecular weight of the copolymer can be adjusted by adjusting the hydrogen and/or polymerization temperature, and the proportion of catalyst components used.

The α-olefin random copolymer obtained by the method of the present invention is different from those previously proposed in that it is non-sticky and has various other properties as described above. This α-olefin random copolymer can be formed into pipes, films, sheets, hollow containers, and various other products by any forming method such as extrusion molding, blow molding, injection molding, press molding, and vacuum forming, and can be used for various purposes. It can be provided to In particular, it is suitable as a packaging film because of its good transparency, blocking resistance, and heat sealability. Due to the above properties, it can also be suitably used as a protective film for metals and the like.

During molding, various stabilizers, antioxidants, ultraviolet absorbers,
Antistatic agents, lubricants, plasticizers, pigments, and inorganic or organic fillers can be incorporated. Examples of these are 2,
6-not-tart-butyl-p-cresol, tetrakis[methylene-3-(3,5-tart-butyl-4-hydroxyphenyl)gropionate]methane, 4
．． 4'-butylidene bis(6-tart-butyl-
cresol), toco-7 dirolles, ascorbic acid, solauryl thionoglobionate, phosphoric acid stabilizer, fatty acid monoglyceride, N,N-(bis-2-hydroxyethyl)alkylamine, 2-(2'-hydroxy) -S
/, S/-not-butylphenyl)-5-chlorobenzotriazole, calcium stearate, magnesium oxide, magnesium hydroxide, alumina, aluminum hydroxide, silica, hydrotalcite, talc,
It may be clay, gypsum, glass fiber, titania, calcium carbonate, carbon black, petroleum resin, polybutene, wax, synthetic or natural rubber, etc.

The α-olefin random copolymer obtained by the method of the present invention can be added to various thermoplastic resins with modifiers, such as modifiers that improve impact resistance, especially low-temperature impact resistance, bending resistance, and low-temperature heat sealability. It can be blended as a quality agent.

By blending the α-olefin random copolymer obtained by the method of the present invention with other ethylene polymers containing ethylene as a main component, such as polyethylene, the impact resistance of molded articles of other ethylene polymers can be improved. , low-temperature impact resistance, bending resistance, and low-temperature heat sealability can be improved.

Other ethylene polymers mentioned above include high density polyethylene, medium density polyethylene, low density polyethylene, ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-27tene, 1-octene, 1-decene. , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. The present invention is a copolymer with an α-olefin having 6 to 20 carbon atoms, and contains ethylene as a main component. Examples include ethylene copolymers obtained by methods other than the above method.

Limiting viscosity [η] measured in decalin at 165°C
is usually in the range of 0.5 to 2 (3 dl/97).

When the α-olefin random copolymer obtained by the method of the present invention is blended with the other ethylene polymer, the blending ratio is usually 1 to 100 parts by weight per 100 parts by weight of the ethylene polymer. ranges from 2 to 60 parts by weight. The resulting ethylene polymer composition may contain antioxidants, hydrochloric acid absorbers, anti-aggregation agents,
Various additives such as heat stabilizers, ultraviolet absorbers, lubricants, weather stabilizers, antistatic agents, nucleating agents, pigments, and fillers can also be blended. The mixing ratio is appropriate.

The ethylene polymer composition can be prepared according to conventionally known methods.

Furthermore, by blending the α-olefin random copolymer obtained by the method of the present invention with a crystalline olefin polymer other than the other ethylene polymer, molded products made of the crystalline olefin polymer can be formed. Impact resistance, especially low-temperature impact resistance, can be improved. Furthermore, a film with well-balanced resistance, blocking properties, transparency, and slip properties can be obtained. Specifically, the crystalline olefin polymer other than the ethylene polymer includes polypropylene, poly-1-butene, poly-4-methyl-1-bentene, propylene-ethylene copolymer, propylene・Like 1-butene copolymer, 1-butene/ethylene copolymer, 1-butene/progylene copolymer, etc.
α-olefins (α,) such as propylene, 1-butene, 1-hexene and ethylene, propylene, 1-butene,
1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1
-Crystalline α-olefin consisting of an α-olefin (α,) having 2 to 20 carbon atoms, such as hexadecene, 1-octadecene, 1-eicosene, which is different from the above α-olefin (α,) Examples include α-olefin copolymers. Intrinsic viscosity [η] of the crystalline olefin polymer measured in decalin at 135°C
is usually in the range of 0.5 to 1Q di/f, and the crystallinity is 5% or more, preferably 20% or more.

When blending the α-olefin random copolymer obtained by the present invention with the crystalline α-olefin polymer, the blending ratio is based on 100 parts by weight of the crystalline α-olefin polymer. It is usually in the range of 1 to 100 parts by weight, preferably 2 to 60 parts by weight. The crystallinity α
- The olefin polymer composition may contain antioxidants, hydrochloric acid absorbers, anti-aggregation agents, heat stabilizers, ultraviolet absorbers, lubricants, weather stabilizers, antistatic agents, nucleating agents, pigments, and fillers, as necessary. It is also possible to mix various additives such as.

The crystalline α-olefin polymer composition can be prepared according to conventionally known methods.

Furthermore, the α-olefin random copolymer obtained by the method of the present invention can be blended with a commonly used engineering resin to improve the physical properties of the engineering resin, such as impact resistance, especially low-temperature impact resistance, and sliding properties. It can be improved.

When the engineering resin is an engineering resin having a susceptibility group, in order to improve the affinity or dispersibility for the engineering resin, the α-olefin random copolymer obtained by the method of the present invention,
Modified α- which is a graft copolymerization of unsaturated carboxylic acids or their derivative components such as maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, dimethyl maleate, trimethyl citraconate, and trimethyl itaconate. Preferably, an olefinic random copolymer is used. The grafting ratio of the unsaturated dicarboxylic acid or its derivative component is usually in the range of 0.02 to 50 parts by weight based on 100 parts by weight of the α-olefin random copolymer. Specific examples of engineering resins include polyesters such as polyethylene terephthalate and polybutylene terephthalate, hexamethylene asonomide, octamethylene asonomide, decamethylene ano/4'mide, dodecamethylene azinone mide;
1? Examples include polyamides such as ricaprolactone, polyarylene oxides such as polyphenylene oxide, polyacetals, ABSlAES, and polycarbonates. The blending ratio of the α-olefin-based silundum copolymer or its modified product is usually 0.2 to 20 fi per 100 parts by weight of the ensoneering resin.
This is the range of part i. The en-soneering resin composition may contain an antioxidant, a hydrochloric acid absorber, an anti-aggregation agent,
Various additives such as heat stabilizers, ultraviolet absorbers, lubricants, weather stabilizers, antistatic agents, nucleating agents, pigments, and fillers can be blended. . The engineering resin composition can also be prepared according to conventionally known methods.

The α-olefin random copolymer obtained by the method of the present invention can be blended with various rubbery polymers to improve the physical properties of the rubbery polymers, such as chemical resistance and rigidity. Specifically, the rubbery polymer includes, for example, ethylene/propylene/non-conjugated tzene copolymer, ethylene/1-butene/non-conjugated diene copolymer,
Examples include I-liptatene rubber, polyisoprene rubber, butadiene-styrene block copolymer in styrene, and the like. The blending ratio of the α-olefin random copolymer is usually in the range of 1 to 100 parts by weight based on 100 parts by weight of the rubbery polymer. Various fillers such as a filler, a crosslinking agent, a crosslinking aid, a pigment, and a stabilizer can be added to the sticky polymer composition as required. The rubbery polymer composition can be prepared according to conventionally known methods.

〔Example〕

Next, the method for producing the α-olefin random copolymer of the present invention will be specifically explained with reference to Examples.

Example 1 (α) Ethylene bis(indenyl) zorconium A 400° glass flask which had been sufficiently purged with nitrogen was charged with 100° tetrahydrofuran, and then cooled to -195°C. And turconium tetrachloride 8.2? was added, and the temperature was gradually raised to room temperature to form a suspension. continuation,
Lithium salt of bis(indenyl)ethane (raf, /, Organo
mgtal, Chum,.

232.255 (1982)), add 55 mmol,
The mixture was stirred at 20°C for 2 hours. Thereafter, hydrogen chloride gas was blown in for several seconds, and then tetrahydrofuran and hydrogen chloride gas were immediately removed under reduced pressure to obtain a solid. The solid was dissolved in 10% hydrochloric acid,
Washed with water, ethanol and soethyl ether and dried under reduced pressure. 4.92 ethylene bis(indenyl)
Zolconium chloride was obtained.

(b) Preparation of ethylene bis(4,5,6,7-tetrahydro-1-indenyl) zirconium chloride Bis(indenyl) zirconium chloride in ethylene synthesized above in a stainless steel autoclave 4
．． 5F, platinum oxide-cut 300■ and dichloromethane 10
After charging 0tR1, hydrogen was introduced to make 100 #/d-guno. Hydrogenation reaction was carried out at 20°C for 1 hour. After the reaction mixture was transferred into 11 dichloromethane, platinum oxide (2) was poured into the solution and dichloromethane was removed to obtain a solid. After washing this solid with petroleum ether,
By recrystallizing with hot toluene, ethylene bis(4
, 5,6,7-tetrahydro-1-indenyl) zolconium cyclolide 2.9f fl.

y in a glass flask of 21 which was sufficiently purged with argon.
gct, .6H,0709 and toluene 625- were charged, and after cooling to 0°C, 1.25 mol of trimethylaluminum diluted with toluene 625- was added dropwise. After the dropwise addition was completed, the temperature was raised to 60°C and the reaction was continued at that temperature for 96 hours.

After the reaction, solid-liquid separation was performed by filtration, and the separated liquid was used for polymerization as an aluminoxane solution. Toluene was removed from a portion of the separated liquid to prepare a sample for molecular weight measurement. The molecular weight determined by freezing point depression in benzene was 1570, and the molecular weight of the aluminoxane was 25.

(Polymerization: Purified toluene 2011 propylene 10 k
& (238 mol) and 2.9 kl of ethylene? (10
4 mol) at -15°C, followed by methylaluminoxane corresponding to 0.4 gram atom in terms of narminiram atom, ethylene bis(4,5, 617-tetrahydro-1-indenyl)zolconium chloride was charged, and polymerization was carried out at -15°C for 5 hours. Polymerization was stopped by adding a small amount of methanol to remove unreacted propylene and ethylene. Furthermore, after removing the catalyst residue with hot water to which a small amount of sulfuric acid and methanol were added, the polymerization solution was poured into a large amount of methanol to precipitate a polymer.

He further washed the precipitated polymer with methanol, 100
It was dried under reduced pressure at ℃ overnight. In this way, a 1230F copolymer was obtained. ``The ethylene content of the copolymer measured by C-NMR is 41.8 mol%, and the intrinsic viscosity [η] determined in decalin at 135°C is 2.BOdl/?
M w / M n determined by GPC is 2.42, DS
The Cp point is 64°C, the crystallization rate determined by X-ray diffraction method is 9%, and the B value determined by IsC-NMR is 1.
It was 26. In addition, the boiling methyl acetate soluble content is 0.04
Weight%, soluble content in acetone/n-decane mixed solvent is 0.2
2% by weight, stress at break 10kg/d, elongation at break 1
100%, JISA hardness is 45, haze is 9%, "C-"
The microisotacticity determined by NMR is 0.95.
Met. The C-NMR spectrum of the obtained copolymer shows αβ, which is based on methylene chains between two adjacent tertiary carbon atoms.

No βr signal was observed.

Examples 2-8. Comparative Examples 2 and 3 Polymerization was carried out in the same manner as in Example 1, except that the type and proportion of monomers supplied, the polymerization temperature, and the heavy metal time were changed. The +3C-NMR spectrum of the obtained copolymer shows αβ based on methylene chains between two adjacent tertiary carbon atoms.

No βr signal was observed. The polymerization results are shown in Table 1.

Example 9 Ethylene bis(indenyl)zorconium cyclolide synthesized in the same manner as in Example 1. Example 1 except that 0.45 mm J gram atoms were used in terms of zirconium atoms and the polymerization time was 10 hours. Polymerization was carried out in the same manner. The "C-NMR spectrum" of the obtained copolymer contains two adjacent
αβ, βγ based on methylene chains between tertiary carbon atoms
No signal was observed.

The results of the first batch are shown in Table 1.

Example 10 Ethylene bis(indenyl) solconium monochrome IJ)'t-/ruconium atom was synthesized in the same manner as in Example 1 except that 0.45 μIJ gram atom was used and the polymerization time was 50 hours. Polymerization was carried out in the same manner as in Example 5.

The "C-NMR spectrum" of the obtained copolymer shows "αβ" based on the methylene chain between two adjacent tertiary carbon atoms.
, no βγ signal was observed.

Comparative Example 1 Preparation of titanium catalyst Commercially available anhydrous magnesium chloride 20t1 Ethyl benzoate4
．． 5 m, 5.0 ml of methylpolysiloxane was placed in a stainless steel ball (diameter 15 feet) 2,8 k1 in a nitrogen atmosphere.
7 was placed in a stainless steel pot with a content of fjt800-, and pulverized and brought into contact for 12 hours under an impact acceleration shield of 7G.

Next, the obtained solid treated product 102 was mixed with titanium tetrachloride 100
It was suspended in mff and reacted at 80°C for 2 hours. After the reaction was completed, the solid portion was thoroughly washed with hexane. In this way, a titanium catalyst containing 2.0% by weight of titanium and 6.5% by weight of ethyl benzoate was obtained.

Polymerization 30J of N-made decane was charged into a stainless steel autoclave with an internal volume of 100J that had been fully substituted with 9 elements, and propylene-
Ethylene mixed gas (propylene/ethylene molar ratio 7
5/25) for 19kl? /hr and hydrogen 801/
After raising the temperature to 60°C by passing the mixture at a flow rate of 100 m, triethylaluminum was charged at 25 milligram atoms in terms of aluminum atoms, 85 millimoles of methyl p-toluate, and the titanium catalyst was charged at 0.5 milligram atoms in terms of titanium atoms. Polymerization was started for 15 minutes. The subsequent operations were performed in the same manner as in Example 1. In this way 14502
A copolymer was obtained. The results are shown in Table 1.

Comparative Example 4 5 kg (89 moles) of 1-butene and 40 r (1.4 moles) of ethylene were placed in a stainless steel autoclave with contents 9201.
and hydrogen 2.5? <1.2 mol) at room temperature, followed by soethylaluminum chloride equivalent to 20 milligram atoms in terms of aluminum atoms, and titanium trichloride (Toho Titanium Products, TAC-151) equivalent to 10 milligram atoms in terms of titanium atoms. ) was charged to start polymerization. Polymerization was carried out at 70°C for 1 hour. The subsequent operations were performed in the same manner as in Example 1. In this way, copolymer 7502 was obtained. The results are shown in Table 1.

Claims (1)

[Scope of Claims] 1. α-olefin having 3 or more carbon atoms and ethylene, (A) at least two groups selected from the group consisting of an indenyl group, a substituted indenyl group, and a partially hydrogenated product thereof are lower Copolymerizing in the presence of a catalyst formed from a transition metal compound of group IVB of the periodic table having a polydentate compound bonded via an alkyl group as a ligand, and (B) aluminoxane, A method for producing an α-olefin random copolymer, characterized in that a copolymer having a content of the α-olefin component of 30 to 99 mol % is obtained.