JPS62121711A - Lowly crystalline ethylene random copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the title copolymer narrow in both MW distribution and composition distribution and excellent in transparency, surface nonstickiness and mechanical properties, by copolymerizing ethylene with a 3-20C alpha-olefin and a 5-20C nonconjugated polyene. CONSTITUTION:Ethylene (A) is copolymerized with a 3-20C alpha-olefin (B) and a 5-20C nonconjugated polyene (C) (e.g., dicyclopentadiene) in the presence of a catalyst comprising a zirconium hydride compound in which the ligand is a group having conjugated pi electrons and an aluminooxane of formula I or II (wherein R is a hydrocarbon group and m>=25). In this way, the title copolymer containing 50-95mol% component A, 5-50mol% component B and 0 (not inclusive) -5mol% component C, having an intrinsic viscosity of 0.5-10dl/g, a MW distribution <=3 (GPC), a crystallinity <=30% and a boiling methyl acetate-soluble portion <=2wt% and satisfying the relationship: 1.00<=B<=2 [wherein B is a value of formula III (wherein PE is the molar fraction of an ethylene component except one derived from the component C in the copolymer, PO is the molar fraction of component B and POE is the molar fraction of B-A chains in the total dyad chains) is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a low-crystalline ethylene random copolymer and a method for producing the same. More specifically, the present invention relates to a low-crystalline ethylene-based random copolymer having a narrow molecular weight distribution and composition distribution and excellent transparency, surface non-adhesiveness, and mechanical properties, and a method for producing the same.

[Conventional technology]

Conventionally, low-crystalline ethylene/α-olefin/non-conjugated polyene copolymers such as ethylene/propylene/non-conjugated tsene copolymer rubber have been used for molding elastic polymers that require weather resistance and heat resistance, or for various resins. Demand is increasing for uses such as modifiers. The production method involves using ethylene,
Methods of copolymerizing α-olefins and nonconjugated polyenes are known. Low-crystalline ethylene/α-olefin/non-conjugated polyene copolymers obtained with titanium-based catalysts generally have poor random copolymerizability, wide molecular weight distribution and composition distribution, and have six clarity, surface non-depletion, and mechanical properties. is inferior.

In addition, low-crystalline ethylene obtained with vanadium-based catalysts
α-olefin/non-conjugated polyene copolymers have improved random copolymerizability, narrower molecular weight and composition distributions, and significantly improved transparency, surface non-adhesion, and mechanical properties compared to those obtained using titanium-based catalysts. However, these properties are still insufficient for applications that require strict requirements, and low-crystalline ethylene α-
Olefin/non-conjugated polyene copolymers are required.

On the other hand, a catalyst comprising a turconium compound and an aluminoxane has been proposed as a new Ziegler type olefin polymerization catalyst in the following series of prior art documents. but,
None of these prior art documents contain any description that specifically suggests a low-crystalline ethylene/α-olefin/nonconjugated polyene copolymer.

JP-A-58-19.5 CI No. 9 describes the following formula (%), where R is cyclopentanoyl, C1~Cs-fulkyl, Norron-TniaF), and Me is a transition metal. , Rαl is ノ・口RN, and a transition gold maple-containing compound represented by the following formula (% formula %), where R is methyl or ethyl, and n is a number from 4 to 20. In the presence of a catalyst consisting of a linear aluminoxane or a cyclic aluminoxane represented by the following formula % Formula % where R and n are the same as above, α- of ethylene and C5 to C1, A process is described in which one or more olefins are polymerized at temperatures between 150°C and 200°C. The publication states that in order to adjust the density of the resulting polyethylene, the polymerization of ethylene should be carried out in the presence of a small amount of a somewhat long-chain α-olefin or a mixture of up to 10%. .

Japanese Patent Application Laid-open No. 59-95292 describes the following formula, where n
is 2-40 and R is C8-C6 alkyl, and a linear aluminoxane of the following formula where n
The invention relates to a method for producing a cylindrical aluminoxane represented by the following, in which the definitions of and R are the same as above. The publication states that when olefin polymerization is carried out by mixing, for example, methylaluminoxane produced by the same production method with a titanium or zirconium bis(cyclopentanoenyl) compound, the amount of olefin produced per 1 ton of transition metal and per hour is , it is stated that more than 25 million 2 polyethylene can be obtained.

JP-A-60-35005 describes the following formula where R
1 is C1-C3° alkyl, and Ro is R' or combined to represent 10-. First, an aluminoxane compound represented by the following is reacted with a magnesium compound, and then the reaction product is chlorinated, and further Ti, A method for producing an olefin polymerization catalyst by treatment with a V, Zr or C de compound is disclosed. The publication states that the above catalyst is particularly suitable for copolymerizing a mixture of ethylene and a C1-C22 α-olefin.

JP-A No. 60-35006 discloses a catalyst system for producing a reactor-blended polymer containing different bi-, mono- or tri-cyclopentasoenyl or a derivative thereof (a) and an alumoxane. (aluminoxane) (b) combinations are disclosed. In Example 1 of the same publication, ethylene and propylene were polymerized using bis(pentamethelcyclopentasoenyl)turconium methyl and alumoxane as catalysts, and the number-average molecule ('11
5,300, a weight average molecular weight of 36.400 and a propylene content of 31.4%. In addition, in Example 2, ethylene and propylene were polymerized using bis(pentamethylcyclopentanoenyl) zircony rhamnofluoride, bis(methylcyclopentasoenyl) zircony rhamnofluoride, and alumoxane as catalysts, and the average molecular weight 2,200, weight 1
J average molecular weight 1j, a toluene soluble portion containing a propylene component of 900 and 30 mol% and a number average molecule [3000,
weight average molecular weight Z400 and number average molecular weight 2, consisting of a toluene insoluble portion containing a propylene component of 4.8 mol%;
000, a weight average molecular weight of 8.300, and a blend of polyethylene and ethylene-propylene copolymer containing a propylene component of 71 mol%. Similarly, Example 5 has a molecular weight distribution (Mw/un) of 4.57, a soluble portion of propylene component of 20.6 mol%, and a molecular weight distribution of 3.
．． A blend of LLDPE and ethylene-propylene copolymer comprising 2.9 mole % of the insoluble portion is described.

JP-A No. 60-45007 discloses that ethylene alone or together with an α-olefin having 5 or more carbon atoms, metallocene and the following formula (%), where R is an alkyl group having 1 to 5 carbon atoms, n is 1
Polymerized in the presence of a catalyst system comprising a cyclic alumoxane or a linear alumoxane represented by the following formula %, which is an integer of ~20, or a linear alumoxane represented by the following formula %, where R and n are defined as above. It describes how to do this. According to the description in the same publication, the polymer obtained by this method has a molecular weight of 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.

In addition, Japanese Patent Application Laid-Open No. 60-35008 states that there is a small <,! :
It has been described that polyethylene or copolymers of ethylene and C5-C7 α-olefins with a broad molecular distribution can be produced by using a catalyst system containing 2%1 metallocene and alumoxane. . The publication describes that the above copolymer has a molecular weight distribution (Mw/un) of 2 to 50.

Furthermore, JP-A-60-35009 discloses a copolymer of ethylene and α-olefin with a small molecular weight distribution (Mw/M n ) of less than 2 by using a catalyst system containing a vanasium compound and an organoaluminum compound. A method of manufacturing is disclosed.

[Problem that the invention seeks to solve]

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

Another object of the present invention is that the molecular weight distribution and composition distribution are narrow;
The object of the present invention is to provide an ethylene-based random copolymer that has excellent 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 that is excellent in mechanical properties such as stress at break and elongation at break.

Still another object of the present invention is to provide a method for producing the low crystalline ethylene random copolymer of the present invention.

Further objects and advantages of the present invention will become apparent from the description below.

[In the formula, P8 indicates the mole fraction of the ethylene component derived from the non-conjugated, dIJene component in the copolymer, P indicates the mole fraction of the α-olefin component, and POE is Indicates the mole fraction of α-olefin/ethylene chains in all dyαd buttons]

The B value expressed by the following formula 0N) is in the range satisfying 1.00≦B≦2...(m), and (fJ'') In the C-NMR spectrum, adjacent (g) A low-crystalline ethylene system characterized by a boiling methyl acetate soluble fraction of 2.0% by weight or less, in which αβ and βγ signals based on a methylene chain between two tertiary carbon atoms are not observed. This is achieved by combining one random system.

The low crystalline ethylene random copolymer of the present invention is
According to the present invention, in the presence of a catalyst consisting of (,4) a zolconium hydride compound having a group having conjugated π electrons as a ligand and (13) an aluminoxane, 2
It can be produced by the method of the present invention in which an α-olefin of 0.0 and a nonconjugated polyene of 5 to 20 carbon atoms are copolymerized.

The zolconium hydride compound (A) using the group having conjugated π electrons as a ligand has, for example, the following formula αI R'R"R" Z r II ..α1
) Here, RI represents a cycloalkasoenyl group, and R1
and R3 is a cycloalkasoenyl group, an aryl group, an alkyl group, a halocarbon atom, or a hydrogen atom.

Cycloalkasoenyl 2tld, such as t-hacyclobentasoenyl group, methylcyclopentagenyl group, ethylcyclopentagenyl group, somethylcyclopentasoenyl group, indenyl group, tetrahydroindenyl group, etc. Examples of the alkyl group of R1 and Bs include methyl group, ethyl group, propyl group, improgyl group, butyl group, etc., and examples of the aryl group include 7-enyl group, benzyl group, neophyl group, etc. Examples of the halodane atom include fluorine, chlorine, and bromine. Examples of the zirconium hydride compound include the following compounds.

Bis(cyclopentagenyl)zorconium monochloride monohydride, Bis(cyclopentagenyl)zirconium monopromide monohydride, Bis(cyclopentagenyl)methylturconium hydride, Bis(cyclopentagenyl)ethyl turco hydride, bis(cyclopentagenyl)cyclohexylturconium hydride, bis(cyclopentagenyl)phenylturconium hydride, bis(cyclopentagenyl)penzylturconium hydride, bis(cyclopentagenyl)neo hydride zirconium hydride, bis(methylcyclopentadienyl) turconium monochloride monohydride, bisindenyl turconium monochloride monohydride. It is preferable to use a compound that is sparingly soluble in a solvent such as toluene, such as cyclopentadienyl)zolconium monochloride monohydride, after contacting it with an organoaluminum compound. By this operation, a zirconium hydride compound that is poorly soluble in a solvent can be made easily soluble in a solvent.

Specifically, the organoaluminum compound to be brought into contact with the above-mentioned zolconium hydride compound includes trialkyl aluminum such as trimethylaluminum, triethylaluminum, and tributylaluminum, trialkenylaluminum such as triisoprenylaluminum, and somethylaluminum methoxide. In addition to noalkylaluminum alkoxides such as aluminum ethoxide and sibutylaluminum butoxide, alkylaluminum sesquialkoxides such as methylaluminum sesquimethoxide and ethylaluminum sesquiethoxide, /? ', 5At (0/?l). Partially alkoxylated alkylaluminium, trimethylaluminum chloride, having an average composition represented by , etc.
So-alkylaluminium halide such as soethylaluminum chloride, trimethylaluminum bromide, alkylaluminum sesquihalide such as methylaluminum sesquichloride, ethylaluminum sesquichloride, alkylaluminum buckwheat such as methylaluminum dichloride, ethylaluminum dichloride Examples include partially halodanized alkyl aluminum such as Ride.

The reaction of both compounds is preferably carried out in a hydrocarbon medium while blocking light, and the mixing molar ratio (Al/Zr) of the organoaluminum compound and the zirconium compound is 0.5 to 3.
0, preferably 1 to 20, and the concentration of zirconium is 0.001 to 1 mol, preferably o
, o o s to about 0.1 mol, and the reaction temperature is set to about O to 120° C. and the two are brought into contact with each other. The hydrocarbon medium can be selected from those exemplified as the polymerization solvent described later.

The aluminoxane (l) of the catalyst component used in the method of the present invention is specifically represented by the general formula ■ or the general formula M and m is 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, a butyl group, and is preferably a methyl group or an ethyl group, particularly preferably a methyl group, and is usually an integer of 25 or more. It is preferably an integer of 30 or more, particularly preferably an integer of 55 to 100.

The following method can be exemplified as a method for producing the aluminoxane.

fl) Compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride hydrate, sulfuric acid hydrate,
A method of adding trialkylaluminium to a carbonized scale medium suspension such as aluminum sulfate hydrate and causing a reaction.

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

Among these methods, it is preferable to adopt method +1+. Note that the aluminoxane may contain a small amount of organometallic component.

In the method of the present invention, the raw material supplied to the polymerization reaction system is a mixture consisting of ethylene, an α-olefin having 6 to 20 carbon atoms other than ethylene, and a nonconjugated 417 dyne having 5 to 20 carbon atoms. The content of ethylene in the polymerization raw material olefin is usually 20 to 90 mol%, preferably 30 to 80 mol%, and the content of α-olefin is usually 1
0 to 80 mol%, preferably 20 to 70 mol%
Furthermore, the content of non-conjugated polyene is usually 1
×10″″4 to 5 mol%, preferably 5×10−4
The range is from 3 mol % to 3 mol %.

Specifically, the α-olefin having 6 to 20 carbon atoms other than ethylene used as a polymerization raw material in the method of the present invention includes propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. , 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-
Examples include octadecene and 1-eicosene. Further, specific examples of the non-conjugated polyene include 1,4-hexanoene, 1.5-hexatsuene, 1,4-pentatsuene, 1
．． 7-octadecene, 1,8-nonatsuene, 1゜9-decatsuene, 4-methyl-1,4-hexatsuene, 5-methyl-1,4-hexatsuene, 5-ethylidene-2-norbornene, socyclopentadiene, 5- Vinyl-2-
norbornene, 5-methylene-2-norbornene, 1,
Examples include 5-cyclooctatsuene, 5,8-endomethylene hexahydronaphthalene, and the like.

In the process of the invention, the olefin polymerization reaction is usually carried out in a hydrocarbon medium. Specifically, the hydrocarbon medium includes aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octa/, decane, dodecane, hexadecane, and octadecane, and aliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane. In addition to hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xene, and petroleum fractions such as gasoline, kerosene, and light oil, the raw material olefin also serves as a hydrocarbon medium. Among these hydrocarbon media, aromatic hydrocarbons are preferred.

In the method of the present invention, a liquid phase polymerization method such as a suspension polymerization method or a solution polymerization method is usually employed, and a solution polymerization method is particularly preferably employed. 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.

When carrying out the method of the present invention by liquid phase polymerization, the proportion of the zirconium hydride compound (, () used is usually 10-
8 to 10-! Durham atoms/l, preferably 10″″
7 to 10-3 gram atoms/! ! is within the range of The proportion of aluminoxane used is usually 10-4 to 10-4 as the concentration of aluminum atoms in the polymerization reaction system.
1 gram atom/l, preferably 10-1 to 5X10
-" Durham atoms/l, and the ratio of aluminum metal atoms to turconium gold M atoms in the polymerization reaction system is usually in the range of 25 to 10?, preferably 102 to 106. Molecular weight of the copolymer can be adjusted by hydrogen and/or polymerization temperature.

In the method of the present invention, the above-mentioned low-crystalline ethylene copolymer of the present invention can be obtained by treating the polymerization reaction mixture after the polymerization reaction has been completed by a conventional method.

The composition of the low-crystalline ethylene random copolymer of the present invention is such that the ethylene component is 50 to 95 mol%, preferably 60 to 95 mol%.
5 to 94 mol%, the a-olefin component is 5 to 5
0 mol %, preferably 6 to 40 mol % and the non-conjugated polyene component is not 0 mol % but less than 5 mol %, preferably in the range of 0.4 to 4 mol %.

Furthermore, the low crystalline ethylene random copolymer of the present invention is
The value of intrinsic viscosity [η] measured in decalin at 135°C is usually 0.5 to 10 dl/g1, preferably 1
to 6 di/g.

Furthermore, the molecular weight distribution (Miw/Mn) of the low-crystalline ethylene random copolymer measured by delvermic acid chromatography (GPC) is 3 or less, preferably 2.5 or less, particularly preferably 2.2 or less. range. When the molecular weight distribution of the low-crystalline ethylene-based random copolymer is greater than 3, the copolymer or a composition containing the copolymer as a modifier becomes more sticky9 or becomes blocking. Therefore, it is necessary to be within the range of 111.

The measurement of the 4n value for M W /
Act like a dog.

(1) Using polystyrene with a known molecular weight (monodisperse polystyrene manufactured by Toyo Soda Co., Ltd.), determine the molecular weight M and its GPC
(Gel Permeation Chromat
ograph) count and molecular weight M and EV
Create a correlation diagram calibration curve for (ElutionVolume). The concentration at this time is 0.02 wt%.

(21GPC croftography of the sample was taken by GPC measurement, and the number average molecular weight M11 and weight average molecular weight M- of polystyrene conversion were calculated according to (1) above, Mw/x
Find the n value. Sample preparation conditions at that time VG l
) The C measurement conditions are as follows.

[Sample preparation]

(a) Aliquot the sample into an Erlenmeyer flask together with 0-dichlorobenzene solvent to a concentration of 0.1 wt%.

(b) Add anti-aging agent 2 to the triangular 7 rasp containing the sample.
．． 0.05 wt% of 6-terL-butyl-p-cresol is added to the polymer solution.

(c) Heat the Erlenmeyer flask to 140'C and stir for about 30 minutes to dissolve.

2) Transfer the liquid to GPC.

(GPC measurement conditions) It was conducted under the following conditions.

(b) Equipment Waters 91 (150C-A L
C/GPC) (B) Column Toyo Soda gI (GMH type) (C) Sample 1400μ! b) Temperature: 140°C (e) Flow rate: 1 mf/in In addition, the low-crystalline ethylene random copolymer has low crystallinity, and its crystallinity determined by X-ray diffraction is 30% or less, preferably 20%. % or less, particularly preferably in the range of 0 to 15%.

Furthermore, the low-crystalline ethylene-based random copolymer of the present invention has the following formula (1) [wherein P is the mole content of the ethylene component containing the ethylene component added to the non-conjugated polyene component in the copolymer. , Po indicates the mole fraction of the α-olefin component, and indicates the mole fraction of the a-olefin/ethylene chain of all dyads.] The B value represented by the following formula (■) 1.00≦ B≦2 (II).

The above B value is an index representing the distribution state of each monomer in the copolymer chain, and is based on J, C, Randall, (M
acromolecules, 15.353 (19
82)), G.

J, Ray (Macromolecules, 1 0+
7 7 3 (1977)), by determining the above constant aPE, Po and P,
Calculated.

E The larger the above B value is, the fewer block-like chains are present, the distribution of ethylene and 1α-olefin is uniform, and the copolymer has a narrow composition distribution.

The low crystalline ethylene-based Langum copolymer of the present invention preferably has the following B value.

1.2-0.2XP ≦B≦1/P 1E
[E More preferably, the general formula ゛1.3-0.3 2001] (IJc-NMR spectrum of a sample in which a polymer was uniformly dissolved in 1+of hexachlorobutanoene) was measured at a measurement temperature of 120" C1 and a measurement frequency of 25.
05MHz, spectral width 1500 H2, filter width 1500Hz, pulse repetition time 4.2 sec,
Measurements were made under the measurement conditions of a pulse width of 7 μSee and a number of transplants of 2,000 to 5,000 times, and from this spectrum, P, P
, P was calculated from 12E 0 0E.

Furthermore, in the 13C-NMR spectrum of the low-crystalline ethylene-based Langum copolymer of the present invention, αβ and βγ based on methylene chains between two adjacent tertiary carbon atoms in the copolymer chain portion are present. No signal observed.

For example, in the copolymer chain part of ethylene and 1-butene, the following bond: C2H5C2Hs is seen from the left tertiary carbon derived from 1-hexane, and the three methylene groups in the center are at positions a, β, and γ from the left. When viewed from the tertiary carbon on the - universal side, they are located at α, β, and γ positions from the right. Therefore, in the above bonding unit, there are methylene groups giving αγ and ββ signals, but there are no methylene groups giving al and βγ signals.

Similarly, in the child bond 2-CH2CH-CI (2CH- Ia I C2Hs C2+15) in which two 1-butenes are bonded with a head and a tail, there is only a methylene group that gives an αα signal, and the αβ and βγ signals are・There is no methylene group that can be produced.

On the other hand, the following bond α β γ δ -CHCH2-CH2CH2-CH, CH-1δ
γ β α I C2HS C21 (5 and α β -CHCH2CH2CH- 1β aI C2H5C2H.

each has a methylene group that gives a signal of βγ and a signal of αβ.

As is clear from the above description, the low crystallinity ethylene copolymer of the present invention has a regular bonding direction of monomers that can form a copolymer with ethylene.

The boiling methyl acetate soluble content of the low crystalline ethylene random copolymer of the present invention is 2% by weight or less, preferably 1.5 to 1.5% by weight.
The range is 0.01% by weight, particularly preferably from 1.0 to 0.03% by weight, particularly preferably from 0.6 to 0.05% by weight. The boiling methyl acetate soluble content [Ex weight %] of the low crystalline ethylene random copolymer is preferably Ex≦2.5-2,0xPE is more preferable, Ex≦1.6-1.2xPE, and particularly preferable is E.
The range is x≦0.85-0.5 XPE.

The amount of boiling methyl acetate extracted was measured by preparing a press sheet with a thickness of 116 m from the sample, and then pressing this press sheet into a 2 + a
The shredded pieces were placed in a cylindrical lath filter and subjected to a Soxhlet extractor for 6 hours at a frequency of about 15 minutes at a time. The extraction amount is
The extracted residue was dried in a vacuum dryer until it reached a constant weight.

The low crystalline ethylene random copolymer of the present invention usually has 0
．． It has a density of 90 g/ec or less. Moreover, the stress at break and the elongation at break are 300 kg/c112 or less and 400% or more, respectively. In addition, the density of the sample is 120"C
The sample was heat-treated for 1 hour and slowly cooled to room temperature over 1 hour, and then measured. Stress at break and elongation at break are JISK-6301
Measured according to.

The iodine value of the low crystalline ethylene random copolymer of the present invention is, for example, 2 to 40, preferably 3 to 30,
It is particularly preferably in the range of 4 to 25.

The low-crystalline ethylene-based random copolymer of the present invention has a narrower molecular weight distribution and compositional distribution than a copolymer obtained using a titanium-based catalyst, and has transparency, surface non-adhesiveness, and mechanical properties. It can be said that it has excellent physical properties. In addition, when compared with the copolymer obtained using a vananoum catalyst, the molecular weight distribution and composition distribution are approximately the same or narrower, but it can be said that the arrangement state in the molecular molecule of the copolymer component is different. .

The low crystalline ethylene run rubber copolymer of the present invention is
As described above, it has very unique properties, so it can be used as a material for various molded products. Also,
By vulcanization, it can be used as a material with even better mechanical strength.

〔Example〕

Next, the method of the present invention will be specifically explained with reference to examples. and 2 mmol of bis(cyclopentanoenyl)norphnium monochloride monohyphenate were charged to form a slurry. 20 mmol and 11 mole of trimethylaluminum (1M solution) diluted with toluene was added dropwise thereto at room temperature.

After the dropwise addition was completed, the temperature was raised to 60°C and the mixture was reacted for 1 hour.

Bis(cyclobentatsuenyl)norphnium monochloride monohyphenate was dissolved in toluene, and the solution turned dark red. Incidentally, the above reaction was conducted with light cut off.

7Narami/Osan's 13°9 g of magnesium chloride hexahydrate and 125 mA of toluene in a 400+L J-Las 7 flask that was fully purged with argon! After cooling to 0℃, toluene 125
250 milliliters of alt' diluted trimethylaluminum was added dropwise. After the dropwise addition was completed, the temperature was raised to 70°C and the reaction was continued at that temperature for 96 hours.

After the reaction, solid-liquid separation was performed by filtration, and toluene was removed from the separated liquid under reduced pressure to obtain 7.3 g of 7-tylamine/oxane as a white solid. The molecular weight determined by freezing point depression in benzene was 1910, and the simple value of the aluminoxane was 31.

During the polymerization, the aluminoxane was redissolved in toluene.

1-Using a continuous polymerization reactor of 2Il of rice, purified toluene wolf
/hr, 7nalfluminoxane in terms of aluminum atoms, 5 milligram atoms/hr, the zirconium catalyst prepared above, in terms of zirconium atoms, lXl0-"milj
Ethylene 3601/I+r, 1- is supplied continuously at the rate of gram atom/hr and simultaneously in the polymerization vessel.
Butene 2401/br and dicyclopentanoene 3g/hr were continuously supplied at a polymerization temperature of 25°C1.
Polymerization was carried out under conditions such as normal pressure, residence time of 1 hour, and polymer concentration of 15 g/g.

The generated polymer solution is continuously extracted from the polymerization vessel,
Stop the polymerization by adding a small amount of methanol,
Furthermore, the polymer solution was transferred into a large amount of methanol, and the precipitated polymer was dried under reduced pressure at 80° C. for 12 hours. Contains ethylene 89.4 mol%, 1-p? Contains ii 9.4 mol%, dicyclopentadiene content 1.2 mol%,
, 41d//g.

Rubber with iodine value 9.5, Mw/Mn=2.13, crystallinity 6.1%, B value 1.09, boiling methyl acetate solution 0.25% by weight, density 0, 888 g/caa' A polymer of the form was obtained. Jl, S K-6 of this polymer
Stress at break, elongation at break, J
IS A hardness and JIS K-6758 tt
, -i 1, Cape-+b 114 1 1- 1
Ding J 1 --41? , L dl:*
+8 I n! u/-is value) are each 11
0 kg/c+++2,980%, 74.2.1%. In the C-NMR spectrum of the obtained polymer, no αβ and βγ coupling due to methylene chains between two adjacent tertiary carbon atoms was observed.The activity per unit zirconium was 1500g-polymer/milligram. The atom was Zr.

Furthermore, 100 parts by weight of copolymer, 5 parts by weight of zinc white, 1 part of stearic acid, 1.5 mff, 55 parts by weight of carbon black, 10 parts by weight of naphthenic oil, 0.5 parts by weight of 2-mercaptopenzothiazole, and tetramethyl 1.5 parts by weight of Nararam monosulfide, 1.5 parts by weight of sulfur. Using an 8-inch oven roll with a ratio of θ weight of 4A parts, the roll temperature is 5.
A blend was prepared by kneading for 30 minutes at 0°C. The vulcanizate obtained by press vulcanizing this formulation at 160'C for 130 minutes was subjected to a tensile test according to 1ISK-6301.

Vulcanized physical properties are 300% monocular 180 kg/0m2
, stress at break 350 kg/0m2, elongation at break 44
0%, and JIs A hardness was 85.

Examples 2 to 6, Comparative Example 1: The same procedure as in Example 1 was carried out except that polymerization was carried out under the conditions shown in &1. In the "C-NMR spectrum" of the obtained polymer, no abnormality at the αβ position or the βγ position due to the methylene chain between two adjacent tertiary carbon atoms was observed. The results are shown in Table 3.

Comparative Example 2 Using a 151 continuous polymerization reactor, purified hexane was
hr, vanadium catalyst made by reacting vananol trichloride and ethanol at a molar ratio of 1/1, 3.5 milligram atoms/)+r in terms of vanadium atoms.

Organoaluminium, which is a mixture of ethylaluminum sesquichloride and ethylaluminum sesquichloride at a molar ratio of 7/3, is 35ml/17g atom in terms of aluminum atom.
Ethylene 380f/hr, 1-butene 2701/hr,
Hydrogen 21/hr and dicyclopentadiene 30g/hr
Polymerization was carried out continuously at a rate of r (Jl) under conditions such as a polymerization temperature of 60°C, a residence time of 1 hour, and a polymer concentration of 70 g/l. At this time, the pressure inside the polymerization vessel was 7.2 k8/c.
It was m2 (Deno). The subsequent cropping was carried out in the same manner as in Example 1.

The C-NMR spectrum of this polymer shows two adjacent
αβ position based on 7 tyrene chain between tertiary carbon atoms, β
A signal at the γ position was observed. The results are shown in Table 3.

Comparative Examples 3 and 4 The same procedure as Comparative Example 2 was conducted except that polymerization was carried out under the conditions shown in Table 2. In the 13C-NMR spectrum of the obtained polymer, signals at αβ and βγ positions based on methylene chains between two adjacent tertiary carbon atoms were observed. The results are shown in Table 3.

Example 5 Preparation of titanium catalyst 2g of tetrabutoxytitanium and 20g of anhydrous magnesium chloride were placed in an 800rnlO5US-made kit equipped with a 2.8kycDSUS ball (15mφ).
It was ground for 8 hours under nitrogen atmosphere (vibratory mill).

The co-pulverized material was transferred to 200% ethylene chloride and heated to 80°C.
I heated it for 2 hours. Thereafter, the co-pulverized products were separated and washed with n-decane until free titanium tetrachloride was no longer detected. 21η of titanium atoms were supported in 1 g of the catalyst thus obtained.

Purified decane 11/h using the same polymerization apparatus as in Polymerization Example 1
r, ethylaluminum sesquichloride was continuously fed at a rate of 5 milligram atoms/hr in terms of aluminum atoms, and the titanium catalyst prepared above was continuously fed at a rate of 40.25 milligram atoms/hr in terms of titanium atoms, and ethylene was simultaneously fed in the polymerization vessel. 6001/hr11-butene 1001/hr
r, and 5-ethylidene-2-norbornene10. F
Continuously supplied at a rate of /hr, polymerization 1m degree 110°C
Polymerization was carried out under conditions such as normal pressure, residence time of 1 hour, and polymer concentration of 2211/l. The subsequent operations were performed in the same manner as in Example 1. The activity per unit titanium was 909 polymers/milligram atom Ti. In the l''C-NMR spectrum of the obtained polymer, no signals at the αβ and βγ positions based on methylene chains between two adjacent tertiary carbon atoms were observed.

〔Effect of the invention〕

(1 other person)

Claims (1)

[Scope of Claims] 1. A low-crystalline ethylene-based random copolymer of ethylene, an α-olefin having 3 to 20 carbon atoms, and a nonconjugated polyene having 5 to 20 carbon atoms, comprising (a) The content of the ethylene component is in the range of 50 to 95 mol%, the content of the α-olefin component is in the range of 5 to 50 mol%, and the content of the non-conjugated polyene component is not 0 mol% but 5 mol%. (b) 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 (@M@w/@M@n) determined by gel permeation chromatography is 3 or less, (d) X-ray diffraction The crystallinity determined by the method is 30% or less, and (e) the following formula (I) B≡P_O_E/(2P_O・P_E)...(I) [
In the formula, P_E represents the molar fraction of the ethylene component excluding the ethylene component derived from the non-conjugated polyene component in the copolymer, P_O represents the molar fraction of the α-olefin component, and P_O_E represents the total dyad. The B value represented by [indicates the mole fraction of α-olefin/ethylene chain] is in a range that satisfies the following formula (II) 1.00≦B≦2...(II), and (f)^ In the 1^3C-NMR spectrum, αβ and βγ signals based on methylene linkages between two adjacent tertiary carbon atoms in the copolymer backbone are not observed, and (g) boiling methyl acetate soluble. 2% by weight or less. 2. In the presence of (A) a zirconium hydride compound having a group having conjugated π electrons as a ligand, and (B) a catalyst consisting of aluminoxane, ethylene, having 3 to 2 carbon atoms
(a) The content of the ethylene component is in the range of 50 to 95 mol%, and the α-olefin component is and the content of the non-conjugated polyene component is not 0 mol% but 5 mol% or less, 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 (Mw/Mn) determined by gel permeation chromatography is 3 or less, and (d) crystallization determined by X-ray diffraction method. (e) The following formula (I) B≡P_O_E/(2P_O・P_E) (where P_E is the ethylene component derived from the non-conjugated polyene component in the copolymer. The B value represented by the following formula (II ) 1.00≦B≦2...(II), and (f) In the ^1^3C-NMR spectrum, two adjacent tertiary carbon atoms in the copolymer main chain are present. Ethylene, an α-olefin having 3 to 20 carbon atoms, and a carbon atom, in which αβ and βγ signals based on the methylene chain between are not observed, and (g) the boiling methyl acetate soluble portion is 2.0% by weight or less. A method for producing a low-crystalline ethylene-based random copolymer from non-conjugated polyenes having a number of 5 to 20.