JPH04103649A - Ethylene-pentene-1 copolymer composition and its use - Google Patents

Abstract

PURPOSE:To obtain the title composition containing a specific ethylene-pentene copolymer and (non) crystalline alpha-olefin random copolymer at a definite ratio and capable of providing a film having excellent seal-opening property and transparency. CONSTITUTION:The objective copolymer composition containing (A) an ethylene-- pentene-1 copolymer containing 1-25wt.% pentene-1 and having 0.01-100g/10min melt flow rate and 0.87-0.96g/cm<2> density, in which the ratio (RS) of impact strength to tear strength in take-off direction of a film with 40mu thickness obtained by casting satisfies the equation and (B) (non) crystalline alpha-olefin random copolymer having two or more kinds of alpha-olefin units, at an A:B weight ratio of (99:1) to (60:40), and enabling the preparation of molded articles having good impact resistance and low-temperature heat sealing property.

Description

[Detailed description of the invention]

TECHNICAL FIELD OF THE INVENTION The present invention has excellent unsealability and transparency, as well as impact resistance and
Good low-temperature heat sealability, especially as a packaging film.
Ethylene-pentene-1 copolymer composition suitable for
Regarding its use. Technical background of the invention Polyethylene produced by high pressure method is a polyolefin
It is known as a resin with relatively good transparency,
It is used for purposes such as films and hollow containers. deer
When it comes to film applications, high-pressure polyethylene
is air-cooled inflation, which is often used in normal film forming.
tion method has sufficient transparency, impact resistance, and tear resistance.
It is difficult to produce molded bodies that Such high pressure polyethylene
To improve the properties of ethylene, other polymerizable monomers are added to ethylene.
A method of copolymerizing polymers such as vinyl acetate has been adopted.
ing. By using this method, air-cooled inflation
Forming using the fusion method is easy, but the film machine
The strength and rigidity of the film may decrease, or the film may block.
New problems such as problems with moldability due to
Problems may arise. By the way, it has excellent mechanical strength and is the same as high-pressure polyethylene.
A Ziegler type catalyst is used as a resin with a certain density.
Ethylene and α-oleph with 3 or more carbon atoms produced by
Copolymers with fins are known. However, Ziegler
ethyl alcohol produced using a vanadium-based catalyst as a -type catalyst.
Ren/a-olefin copolymers generally have low melting points.
Therefore, there are problems with heat resistance and mechanical strength. On the other hand, titanium-based solid catalysts and organic
By using an aluminum compound catalyst component,
Compared to copolymers produced using sodium-based catalysts,
Both ethylene and a-olefin have high heat resistance and high heat resistance.
Polymers can be produced. However, α-olef
α-olefin with a relatively small number of carbon atoms
, for example, propylene having 3 carbon atoms or a carbon atom
When butene-1 having 4 molecules is used, this copolymerization
The mechanical strength of the molded body prepared from the body is as high as expected.
It doesn't improve to that degree. Therefore, as an a-olefin,
a-olefins with a relatively large number of carbon atoms, e.g.
By copolymerizing α-olefin of number 6 or more and ethylene,
A molded article with high mechanical strength was obtained. However, this
A molded article, especially a film, formed from a copolymer is
Has very high impact strength, but tear strength
is too high, so if you wrap it with such a film, it will be difficult to open it.
A new problem arises in that sealing becomes difficult. Under these circumstances, the present inventor developed a titanium-based solid catalyst component.
and an organoaluminium compound catalyst component.
and pentene-1, which has 5 carbon atoms, is produced.
This provides excellent impact strength and suitable tear strength (all
In other words, it is possible to obtain a resin that has both excellent unsealability).
are finding. Ethylene prepared using new catalysts as described above
・Pentene-1 copolymer has excellent properties as mentioned above.
This ethylene-pentene-1 copolymer
The body is made of ethylene/σ-olefin, which has been tried before.
It has the potential to further expand the applications of copolymers
. However, this ethylene-pentene-1 copolymer
As a result of the inventor's further study of the characteristics of
Among the excellent properties of polymers, impact resistance and
There is still room for further improvement in terms of heat sealability and low temperature heat sealability.
It turns out that there is something. The present invention provides that the above-mentioned ethylene/pentene-1 copolymer is
without sacrificing its inherently excellent properties.
Ethylene-pentene-1 copolymer with good properties in
Compositions and films formed from the compositions are provided.
It is intended to. More specifically, the present invention has excellent unsealability and transparency.
It is possible to form a film with good impact resistance.
Preparing a molded product with impact resistance and low-temperature heat sealability
Ethylene-pentene-1 copolymer composition and
and to provide a film formed from the composition of the present invention.
The purpose is Summary of the invention The ethylene/pentene-1 copolymer composition according to the present invention is
, (A) Repeating units and pens derived from ethylene
Ethylene with repeating units derived from Ten-1
・A pentene-1 copolymer, and (a) AS
Melt flow measured by TM D 1238E
The rate is 0.01 to 100 g/10 minutes, (b)
Density as measured by ASTM D 1505 is 0
．． 87 to 0.96 g/cm3, and (c) the ethylene
from pentene-1 in pentene-1 copolymer
The content of repeating units induced is 1 to 2 in monomer terms.
5% by weight, (d) the ethylene/pentene-1 copolymer
A 40 μm thick film obtained by molding the combined material into a cast film.
The impact strength of the film and the cracking strength of the film in the pulling direction
The ratio (RS) to the degree is RS≧-20logMFR-1000d+968 (formula
where MFR represents the melt flow rate of the copolymer,
d represents the density of the copolymer)
(B) a ten-1 polymer derived from a different a-olefin.
Both have two types of repeating units, low crystallinity or amorphous
a-olefin random copolymer with 99=1 to 6
It is characterized by containing at a weight ratio (A:B) of 0:40.
are doing. Further, the film of the present invention can be made from ethylene resin as described above.
It is formed from a tenten-1 copolymer composition. The above ethylene/pentene-1 copolymer (A) is highly crystalline.
This highly crystalline copolymer (A
) and a copolymer (B) with low crystallinity or poor quality are used together.
This allows us to form a film with excellent opening and transparency.
It has good impact resistance and low temperature heat resistance.
A composition that can be used to prepare a molded article with sealability
It is possible to do this. And low crystallinity as mentioned above
By blending the extremely inferior copolymer (B),
The tyrene-pentene-1 copolymer (A) basically has
There is no substantial decrease in the properties of DETAILED DESCRIPTION OF THE INVENTION The ethylene/pentene-1 copolymer set according to the present invention will be described below.
The composition will be explained in detail. First, ethylene pentene, which constitutes the composition of the present invention,
1 copolymer (A) will be specifically explained. Ethylene-pentene 1 copolymer constituting the composition of the present invention
Body (A) is a repeating unit derived from ethylene and pentene-1.
It has a repeating unit derived from In this ethylene/pentene-1 copolymer (A)
The content of repeating units derived from pentene-1 is
The monomer equivalent content is within the range of 1 to 25% by weight.
, furthermore, this content should be within the range of 4 to 23% by weight.
is preferably within the range of 6 to 20% by weight.
is particularly preferred. This ethylene/pentene-1 copolymerization
Body (A) is composed of two components: ethylene and pentene-1.
It may be a copolymer formed, and furthermore, this copolymer may be
Other polymerizable components within the range that does not impair the properties of the polymer (A)
It may also be a multi-component copolymer using. This joint weight
In the case where the polymer (A) is a two-component copolymer,
Repeating units derived from ethylene in copolymers
The content rate is necessarily the monomer equivalent content rate, and is
99% by weight, and the content is pentene-1
Depending on the content of repeating units derived from
or 77 to 96% by weight, particularly preferably 80 to 94% by weight
The amount is within the range of %. In addition, if it is a multi-component copolymer,
In this case, this ethylene/pentene-1 copolymer (A
) in α-oles other than ethylene and pentene-1
Repeating units derived from fins or polyenes
The content is usually 10% by weight or less, preferably 5% by weight.
The content is particularly preferably 3% by weight or less. like this
Other a-olefins from which repeating units can be derived
Examples include propylene, 2-methylpropylene,
1-butene, 1-hexene, 4-methyl-1-pentene
, 3-methyl-1-pentene, 1-octene, nonene-
1, decene-1, undecene-1 and dodecene-1
can be mentioned. Poly in this copolymer (A)
Repeating units derived from ene are, for example, butadiene
isoprene, 1,4-hexadiene, dicyclopene
Tagene and 5-ethylidene-2-norbornene, etc.
can be derived from. Ethylene resin, which is composed of the repeating units shown above,
Melt flow rate (M
FR) within the range of 0.01 to 100 g/10 minutes
Furthermore, this MFR must be 0.05
The copolymer (A) within the range of ~50 g/10 minutes is particularly
It is preferably used for. That is, MFR is 0.01g
/ If the time is less than 10 minutes, the moldability of the resulting composition will decrease.
At the same time, films formed from this composition, etc.
The transparency of the molded product decreases. Also, MFR is 100g/
If the time exceeds 10 minutes, the mechanical strength will decrease. Furthermore, this M
FR is a value measured according to ASTM D 1238E
It is. And of this ethylene pentene-1 copolymer (A)
Density ranges from 0.87 to 0.96 g/cm' (7)
It is necessary that the value is within 0.88 to 0.94.
A copolymer (A) having a density of g/Cm' is preferably used.
used. The density here is measured according to ASTM D 1505.
This is the value. Such ethylene/pentene-1 copolymer (A) is
It is a highly crystalline copolymer, and at least
Higher crystallinity than α-olefin random copolymers
have. In other words, θ is determined by X-ray diffraction method.
The degree of crystallinity is usually 25% or more, preferably 30% or more.
It is above. Therefore, such ethylene pentene-1
The copolymer (A) has multiple melting points, and usually
The highest melting point of this copolymer is 110-125°C, preferably
The temperature is within the range of 1.12 to 123°C. And ethylene pentene constituting the composition of the present invention
-1 copolymer (A) has the above-mentioned properties.
At the same time, this copolymer (A) is used to cast a cast filler.
Test film with a thickness of 40 μm obtained by molding
The impact strength of the film and the direction in which this film is taken
The ratio (RS) to the tear strength is the melt flow rate described above.
In the relationship between and density, it is expressed by the formula [+] shown below.
It needs to be larger than a certain value so that the RS ≧-20-MFR-1000d+ 968
- [1 piece However, "- In the notation [+], MFR is
represents the melt flow rate of this copolymer (A), and d is
It represents the density of the copolymer. In addition, RS is as mentioned above.
, the film impact strength of the test film and this film
to the tear strength in the pulling direction, that is, the impact strength/
This is the tear strength value. The ratio (RS) of this impact strength to tear strength is (-207M
Ethylene greater than the value of FR-10006+968)
・By using a pentene-1 copolymer, the present invention
Impact strength and tear of films prepared using the composition of
The balance with strength is very good. That is, R.S.
Ethylene pentene-1 whose ratio satisfies the above formula [+]
Copolymer (A) and a low-crystalline or non-crystalline ethylene
Using a ren/a-olefin random copolymer (B)
For example, the impact strength is strong, but the opening performance is poor.
Alternatively, conventional products may be easy to open but have poor impact strength.
It is possible to solve the problems that have been caused by packaging materials.
It is possible. Furthermore, the value of this RS is expressed by the following formula [1°]
copolymer (A), particularly preferably represented by [1”]
By using the copolymer (A), impact strength
Obtaining a composition with a better balance between strength and tear strength
I can do it. RS≧-20MFR-1000d+ 973
... [l°] 200≧RS≧-20th. MFR-1
000d+975... [1°' Note that the above R
A 40 μm thick test plate used to measure the S value.
The film uses ethylene/pentene-1 copolymer (A).
It was created under the following conditions. In other words, 65mm≠T-die film completely extruded by extruder
Using a molding machine, set the resin temperature under the die to a range of 220 to 240°C.
Within the range, still roll temperature within the range of 30 to 40℃, film formation
Speed (thickness 40pm) in the range of 20-40 m/min
and draft ratio (= film thickness (mm)/
Lip opening (mm) within the range of 0.05 to 0.07
It was prepared by setting and forming a film. In addition, ethylene pen having the characteristics as described in 1.
Obtained by processing Ten-1 copolymer (A) as described above.
The impact strength of a 40 μm thick cast film is usually 1
000kg-cm/cm or more, preferably 1200+
; r·Cm/cm or more. Also, how to take off the film prepared as above
tear strength (TMI)) and the raw material ethylene
Melt flow rate of tenten-1 copolymer (M F R
) preferably satisfies the relationship shown by the following formula [2].
Delicious. -TMD≦-0,377MFR-5,1d +6.72
- [2] However, in the formula, d represents the density of the copolymer. A more preferable relationship is kcw TM+1≦-0,377MFR-5,ld+
6.65 [2'] A particularly preferable relationship is bg T, 4n≦-0,37-)8 MFR-
5,ld + 6.59- [2°゛ko. In this way, tearing in the pulling direction of the film as described above
As shown in the above formula [2], the intensity (T, , ) and MFR are
Ethylene-pentene-1 copolymer that satisfies the relationship
By using (A), impact strength and unsealability can be improved.
Composition of the present invention capable of producing films with excellent balance
Manufacture. In addition, ethylene/pentene-1 copolymer (
Molding according to ASTM D 1928 using A)
Stress-resistant crack of 0.5mm thick pressed sheet
Tsucking property (SC resistance (ESCR), ASTM D 1
Measured according to 692, Anthalosox 100%, 50
°C) is open at 10 o'clock or more, and this ESCR and
rutoflow rate (MFR) and copolymer (A).
The density (d) has the relationship shown by the following formula [3-a]
It is preferable that ESCR≧0.7x 104 (hase80-IQgMFR)
3 (0,952-d) [3-a] However, this formula [3-a] means that MFR is 2.0≦MF
The relationship applied to the copolymer (A) within the range of R≦50
I am in charge. Then, this relationship between the champions satisfies the formula [3°-a].
It is preferable to use a copolymer (A) having the formula [3''
-a] can be used.
Particularly preferred. ESCR≧0.9X 104 (y 80-k)gMF
R)' (0,952-d) [3'-a] ESCR≧1.1 x 10' (tog 80-bg
MFR)' (0,952-d) [3°°-a] In addition, this ethylene-pentene-1 co-fi combination (A)
0 prepared according to ASTM D 1928 using
, Stress cracking resistance of 5mm thick press sheet
ff (it SC (ESCR), ASTM D
1692 Ni semi-m L Te 15111 fixed, Antarosoku
10%, 50℃) for 20 hours or more, and
ESCR, melt flow rate (MFR) and joint
The density (d) of the polymer (A) is represented by the following formula [3-b]
It is preferable that the relationship is such that ESCR≧1.4X 10' (i40 kog MF
R) 2(0,952' d) [3-b] Tatashi, Kono style [3-b] Ha, M F R Ka, 1.0≦
Applicable to copolymers (A) within the range of VFR≦20.
This is a relationship that And the relationship between these three satisfies the formula [3'-b].
It is preferable to use a copolymer (A) having the formula [3''
-b] can be used.
Particularly preferred. ESCR≧1.7X 10' (lcg 40-b8M
FR)2(0,952-d)... [3'-b] ESCR≧2. Ox 10' (log 440-
1o MFR)2(0,952-d)... [3”
-b] Furthermore, this ethylene/pentene-1 copolymer (A)
0 prepared according to ASTM D 1928 using
, 5mm thick press sheet stress resistant crackkin
(SC resistance (ESCR), ASTM D 1692
Measured in accordance with 10% Anthalox, 50℃)
0 hours or more, and this ESCR and melt flow
-rate (MFR) and density (d) of copolymer (A)
have the relationship shown by the following formula [3-c]
is preferred. ESCR≧0.50x 10' (lcw 1100-
b MFR) (0,952-d) [3-c] However, this formula [3-c] means that MFR is 0.1≦MF
Relationship applicable to copolymer (A) within the range of R≦5
It is. And the relationship between these three satisfies the formula [3°-C].
It is preferable to use a copolymer (A) having the formula [3°
Use a copolymer (A) that satisfies ``-C]
is particularly preferred. ESCR≧0.65X 104 (bg 1100-b
MFR) (0,952-d)...[3°-c] ESCR≧0.80X 104 (k8100-k)g
MFR) (0,952-d)...[3''-c] Furthermore, the haze of the press sheet prepared as above
HAZE and melt flow rate (MFR)
The density (d) of
Using ethylene/pentene-1 copolymer (A) with
It is preferable that k) gHAZE≦15d-0,45iog MFR-
12,23・ [4 and the relationship between these champions is the formula [4
It is preferable to use a copolymer (A) that satisfies
Precisely, a copolymer (A) satisfying the formula [4"°] is
Particularly preferred is the use of k) gHAZE≦15d-0,45-MFR-12,2
6-[4°]k) gHAZE≦15d-0,45 MF
R-12,30-[4”] In order to measure the above physical properties,
The press sheet with a thickness of 0.5 mm used for
ASTM D 1 tyrene-pentene 1 copolymer (A)
It was created in accordance with G.928. In addition, the measurement of HAZE value is based on ASTM D 1003.
Measured based on Stress crack resistance of specimens thus prepared
Ethylene petroleum, which has the above relationship between gender and haze.
By using Tenten-1 copolymer (A, ),
Injection molding, rotational molding, blow molding using the composition of the present invention
When preparing molded bodies by
Cracks due to force are less likely to occur. That is, the contents
Can be molded into molded objects that are less likely to cause leakage problems.
Wear. Ethylene-pentene-1 copolymer with the above properties
Coalescence involves ethylene and pentene-1, and if necessary, other
copolymerization of reactive monomers by various methods.
It can be prepared by The following is a description of the method for producing ethylene/pentene-1 copolymer.
Show three examples of ethylene/pentene-1 copolymerization
The method for manufacturing body (A) will be explained. In addition, the ethylene petroleum obtained by these three methods
For convenience, the ethylene-hentene-1 copolymer is
Copolymer [I], ethylene/pentene-1 copolymer [n
], is called ethylene pentene-1 copolymer [m],
Ni-1-lene pentene that can be used in the present invention
These copolymers [+], [n],
Not only [m] but also mixtures of these or other products.
The same applies to the ethylene/pentene-1 copolymer obtained by the method.
It can be used in various ways. First, how to produce ethylene/pentene-1 copolymer [2]
Explain the law. Ethylene/pentene-1 copolymer [I] is a combination of ethylene and
Pentene-1, for example, with the following olefin heavy
Manufactured by copolymerization in the presence of a polymerization catalyst
be able to. Produce this ethylene-pentene-1 copolymer [I]
The catalysts used for olefin polymerization include, for example,
For example, in Japanese Patent Application Laid-open No. 56-811, the applicant
Use of catalysts as disclosed below.
I can do it. That is, for example, as such a catalyst, [A](i)
A magnesium compound in a liquid state that does not have reducing ability, and α
1) A titanium compound in a liquid state, and a titanium compound in a liquid state.
A solid product is formed by contacting the
, the contact is (iii) with no active hydrogen and no 4-electron donor.
or after the contact with the 011) activated water.
obtained by further contacting with an electron donor that does not have an element
Requires magnesium, titanium, halogen and electron donor.
a solid titanium catalyst component contained as an essential component, and [B] an organic compound catalyst component of metals from Groups 1 to M of the periodic table.
Mention may be made of catalysts for olefin polymerization comprising: Here, the above [A] used in the preparation of the solid titanium catalyst component.
Magnesium compounds that do not have the ability to reduce
Gnesium-carbon bond or magnesium-hydrogen bond
It is a magnesium compound that does not have such reduction.
Magnesium compounds that do not have the above-mentioned bond
Derived from magnesium compounds with reducing ability
It may be something that has been Examples of magnesium compounds that do not have such reducing ability
Magnesium chloride, magnesium bromide, magnesium iodide
Magnesium halides such as magnesium and magnesium fluoride. Methoxymagnesium chloride, ethoxymagnesium chloride
, Isopropoxy Magnesium Chloride, Butoxy Magnesium Chloride
Alcohol compounds such as nesium, octoxymagnesium chloride, etc.
simamagnesium halide phenoxymagnesium chloride,
Allyloxima such as methylphenoxymagnesium chloride
Gnesium halide ethoxymagnesium, isopropoxymagnesium,
butoxymagnesium, n-octoxymagnesium,
Alkoximers such as 2-ethylhexoxymagnesium
Gnesium phenoxymagnesium, dimethylphenoxymagnesium
Allyloxymagnesium laurate such as um
magnesium stearate, etc.
Examples include carboxylates. These magnesium compounds that do not have reducing ability
A compound derived from a magnesium compound having
may be a compound derived during the preparation of the catalyst component. Magnesium compounds that have reducing ability are replaced with magnesium compounds that have reducing ability.
For example, in order to derive magnesium compounds from
Converting magnesium compounds with basic properties into polysiloxanes
compound, halogen-containing silane compound, halogen-containing aluminum
Contact with compounds such as aluminum compounds, esters, alcohols, etc.
All you have to do is touch it. Here, as a magnesium compound having reducing ability,
For example, magnesium-carbon bond or magnesium
Name magnesium compounds with mu-hydrogen bonds
I can do it. Magnesium compounds with such reducing ability
Specific examples include dimethylmagnesium, diethylmagnesium, and dipropylene.
pill magnesium, dibutylmagnesium, cyamylma
Gnesium, didecylmagnesium, didecylmagnesium
um, ethylmagnesium chloride, propylmagnesium chloride,
Butyl magnesium chloride, hexyl magnesium chloride,
Amylmagnesium chloride, butyl ethoxymagnesium
, ethylbutylmagnesium, octylbutylmagnesium
um, butylmagnesium halide, etc.
be able to. In addition, the magnesium compound has the above-mentioned reducing ability.
Magnesium compound and non-reducing ability
In addition to compounds, combinations of the above magnesium compounds and other metals are also available.
Complexes, compound compounds or mixtures with other metal compounds
It may be. Furthermore, combinations of two or more of the above compounds
It may also be a combined mixture. Among these magnesium compounds, it does not have reducing ability.
Magnesium compounds are preferred, and halogens are particularly preferred.
It is a magnesium compound containing
But magnesium chloride, alkoxymagnesium chloride,
Allyloxymagnesium chloride is preferably used. These magnesium compounds in liquid form are
Charcoal that is soluble in magnesium compounds
Dissolved in hydrogen chloride solvent, electron donor or mixtures thereof
Preferably, the solution is used. Examples of hydrocarbon solvents used for this purpose are pentane, hexane, heptane, octane, decane,
Aliphatic hydrocarbons such as dodecane, tetradecane, and kerosene
. Cyclopentane, methylcyclopentane, cyclohexa
cyclohexane, cyclooctane, cyclohexane
Alicyclic hydrocarbons such as xene: benzene, toluene,
Aromatics such as xylene, ethylbenzene, cumene, cymene
Aromatic hydrocarbons dichloroethane, dichloropropane, and
Like chlorethylene, carbon tetrachloride, chlorobenzene
Examples include halogenated hydrocarbons. To obtain magnesium compounds dissolved in hydrocarbon solvents
, depending on the type of compound and solvent used.
, a method of simply mixing both, a method of mixing and heating,
Magnesium compounds soluble electron donors, e.g.
Alcohols, aldehydes, amines, carboxylic acids, their
Any mixture or even mixtures of these with other electron donors
Adopt methods such as making a compound exist and heating it as necessary.
can be used. For example, halogen-containing magnets
The compound is dissolved in a hydrocarbon solvent using alcohol.
The types of hydrocarbon solvents and their use
Depending on the amount or type of magnesium compound, etc.
Although different, alcohols are halogen-containing magnesium
Usually 1 mol or more, preferably about 1 to 1 mol per mol of the compound
about 20 moles, particularly preferably in the range of about 1.5 to about 12 moles.
It is used as a percentage. Aliphatic hydrocarbons as hydrocarbons
and/or when using alicyclic hydrocarbons, the above
Alcohol can be used in the proportion of especially carbon
Magnesium compounds for alcohols with 6 or more atoms
Due to its high solubility, the amount of such alcohol used is
, about 1 mol or more per 1 mol of halogen-containing magnesium
, preferably at a ratio of about 1.5 mol or more.
Wear. Therefore, halogen-containing products can be produced with only a small amount of alcohol.
Magnesium compounds can be solubilized and active
It is preferable because it becomes a catalyst component with a large amount. In this case,
For example, if only alcohols with 5 or fewer carbon atoms are used, ha
Approximately 15 mole per mole of rogen-containing magnesium compound
of alcohol is required, and the catalytic activity is also higher than that of the above system.
It's not as good as that. On the other hand, aromatic hydrocarbons are used as hydrocarbons.
If so, regardless of the type of alcohol,
of halogen-containing magnesium compounds depending on the amount of alcohol used.
Solubilization is possible. Contact of halogen-containing magnesium compounds with alcohol
is preferably carried out in a hydrocarbon medium, usually at or above room temperature.
, about 65°C or higher depending on the type of hydrocarbon medium, preferably
preferably about 80 to about 300°C, more preferably about 100 to about 300°C
At a temperature of about 200°C, about 15 minutes to 5 hours, more preferably
This is done by keeping the product in contact for about 30 minutes to 2 hours.
. Suitable number of carbon atoms for the alcohol used here: 6
Examples of the above alcohol include 2-methylpene
Tanol, 2-ethylbutanol, n-heptatool,
n-octatool, 2-ethylhexanol, decanol
dodecanol, tetradecyl alcohol, undecanol,
Senol, oleyl alcohol, stearyl alcohol
aliphatic alcohols such as. Benzyl alcohol, methylbenzyl alcohol, iso
Propylbenzyl alcohol, a-methylbenzyl alcohol
Aromatics such as kohl, a,a-dimethylbenzyl alcohol
Aromatic alcohol: n-butyl cellosolve, 1-butoxy-2-propate
Aliphatic alcohols containing alkoxy groups such as
I can give an example. Examples of other alcohols include methanol, ethanol,
propatool, butanol, ethylene glycol, methane
Alcohols with 5 or fewer carbon atoms, such as lucarpitol
can be exemplified. In addition, when using carboxylic acid, the number of carbon atoms is 7 or more.
The above organic carboxylic acids are preferred, such as caprylic acid,
2-Ethylhexanoic acid, undecylenic acid,
Nitric acid, octanoic acid, etc. can be used.
Wear. When using aldehydes, aldehydes with carbon atoms of 7 or more
Preferred are dehydes, such as capricaldehyde,
2-Ethylhexyl aldehyde, undecyl aldehyde
Hido etc. can be used. In addition, when using amines, amines having 6 or more carbon atoms may be used.
Preferably, such amines include, for example,
heptylamine, octylamine, nonylamine, decylamine
laurylamine, undecylamine, 2-ethylamine, laurylamine, undecylamine,
Tylhexylamine and the like can be used. this
When using carboxylic acids, aldehydes and amines such as
Suitable usage amounts and temperatures are described for alcohol.
It is almost the same as Magnesium compounds in combination with soluble electron donors such as those mentioned above.
Examples of other electron donors that can be used include organic acid esters,
Organic acid halides, organic acid anhydrides, ethers, ketones,
3 amine, phosphite, phosphoric acid ester, phosphoric acid
Amides, carboxylic acid amides, nitriles, etc.
For example, specific examples of these are described below (iii)
Using something similar to an electron donor that does not have active hydrogen
I can do it. The hydrocarbon solution of the magnesium compound also contains the magnesium compound.
Other magnesium compounds that can be converted to magnesium compounds
or magnesium metal to the magnesium compound.
Can also be formed by dissolving while converting
It is. For example, the alcohol, amine, aldehyde
, an alkyl group is added to a hydrocarbon solvent in which a carboxylic acid, etc. is dissolved.
, alkoxyl group, alkoxyl group, acyl group, amino
Magnesium compounds with groups, hydroxyl groups, etc., magnesium oxide
Dissolving or suspending ium, magnesium metals, etc.
Hydrogen halides, silicon halides, halogens, etc.
Halogenated with a halogenating agent but without reducing ability
By producing a gen-containing magnesium compound,
Examples include a method of dissolving. Grini again
Jarl's reagent, dialkylmagnesium, magnesium ha
Rusting of hydrides or these with other organometallic compounds
compounds such as M, Mg, R, I, R2qX, Y. (In the formula, M is aluminum, zinc, boron or beryllium.
um atom, R;, R2 is a hydrocarbon group, X, Y is OR
S, O5i R4RSR6, NR) R8, SR9 group
RS, R4, RS, R6, R7, R6 are hydrogen atoms
child or hydrocarbon group, R9 is a hydrocarbon group, a, b
>O, pSq, rXs≧O, b/
If a≧0.5 and the valence of M is m, then p+q+
The formula r + s = ma + 2b is satisfied, and O≦(r + s
)/(a+b)<1.0. ) reduction like
alcohol, ketone, etc.
, ester, ether, acid halide, silanol, silano
Reduction by treatment with a compound that can eliminate the reducing ability such as xane
Magnesium compounds that do not have the ability to dissolve in hydrocarbon solvents
It can also be made into In addition, in preparing the above catalyst, a catalyst that does not have reducing ability was used.
The use of magnesium compounds is essential, but they have reducing ability.
totally excludes the mixed use of magnesium compounds
isn't it. However, considering the activity of the catalyst, catalyst
During production, a large amount of magnesium compound with reducing ability is used.
In many cases, it is not preferable not to use them together. Using a solution of electron donor as a solution of magnesium compound
You can also be there. Electronic devices used for such purposes
Preferred examples of the donor include the alcohols and amines listed above.
, aldehydes and carboxylic acids, especially alco
preferred. Examples of other electron donors are phenol,
Ketones, esters, ethers, amides, acid anhydrides, acid halide
These include nitrile, isocyanate, etc. these
The quantitative relationship and melting temperature when manufacturing a solution are generally determined by electron
The same applies to the case of dissolving in a hydrocarbon solvent using a donor.
, - Since it is necessary to maintain the numerically high temperature, the catalyst preparation
From above, it is easier to use something dissolved in hydrocarbons.
High performance can be obtained easily. Used for the preparation of solid titanium catalyst component [A] (11
) As a titanium compound, for example, T i (OR) 1l
X4-1 (R is a hydrocarbon group, X is a halogen atom, 0≦g≦4)
Mention may be made of the tetravalent titanium compounds shown below. Yo
Specifically, tetrahalogens such as TicR4, TiBr, TiI, etc.
Titanium genide; T i (OCR,) CQ3, T 1 (OC2Hs) CQ s, T 1 (On
C4Hg) CQ s, Ti(OC2H5)B
r,, trihalo such as T1(0-iso-C4H3)Br,
Alkoxytitanium genide; Ti(OCR,), CQ 2 , T l (OC2H5)2 CQ 2 , Ti(On-
C,H,)2Cffi2,'ri(oC2Hs)2B
Dihalocarbonated Schiff Jlzkoxytitanium such as r2: TicoCH,)3C2, Ti(QC2H1), CI! . Monohalogenated thoria such as Ti(On-C4H,), CR, Ti(QC2H5), Br, etc.
Rukoxytitanium; Ti (OCHa)4, 'ri(OC2H,)4, Tj(On-C,H,)4, Ti(0-iso-C,H,)4, Ti(0-2-ethylhexyl) Tetraalcos such as 4
Examples include oxytitanium. Among these, halogen-containing titanium compounds, especially tetra
Titanium halides are preferred, and tetrasalts are more preferred.
Titanium oxide is used. These titanium compounds can be used alone.
may be used, or two or more types may be used in combination.
. Furthermore, these titanium compounds are
or diluted with halogenated hydrocarbon compounds, etc.
Good too. Used in the preparation of [A] solid titanium catalyst component as described above
(iii) As an electron donor without active hydrogen
are organic acid esters, organic acid halides, organic acid anhydrides,
-ter, ketone, tertiary amine, phosphite, phosphorus
acid ester, phosphoric acid amide, carboxylic acid amide, nitric acid ester
For example, Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone
acetophenone, benzophenone, benzoquinone, etc.
Which ketones having 3 to 15 carbon atoms acetaldehyde,
Propionaldehyde, octylaldehyde, benzua
Charcoal such as Rudehyde, Tolualdehyde, Naphthaldehyde etc.
Aldehydes with 2 to 15 atoms Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, vinegar
propyl acetate, octyl acetate, cyclohexyl acetate, propyl acetate
Ethyl pionate, methyl butyrate, ethyl valerate, chlorine vinegar
Methyl acid, ethyl dichloroacetate, methyl methacrylate,
Ethyl crotonate, ethyl cyclohexanecarboxylate,
Methyl benzoate, ethyl benzoate, propyl benzoate,
Butyl benzoate, octyl benzoate, cyclobenzoate
xyl, phenyl benzoate, benzyl benzoate, toluy
Methyl toluate, ethyl toluate, amyl toluate,
Ethyl methylbenzoate, methyl anisate, n-maleate
Butyl, diisobutyl methylmalonate, cyclohexene
Di-n-hexyl carboxylate, diethyl nadic acid, tet
diisopropyl lahydrophthalate, diethyl phthalate,
Diisobutyl phthalate, di-n-butyl phthalate, phthalate
Di-2-ethylhexyl acid, γ-butyrolactone, δ-butyrolactone
Rerolactone, coumarin, phthalide, ethylene carbonate, etc.
An organic acid ester having 2 to 30 carbon atoms. Acetyl chloride, benzoyl chloride, toluic acid
having 2 to 15 carbon atoms such as loride and anisyl chloride
Acid halides: methyl ether, ethyl ether, isopropyl ether
butyl ether, amyl ether, tetrahydrofu
Lan, anisole, diphenyl ether epoxy-p-
Ethers with 2 to 20 carbon atoms such as menthane or
are diethers; acetic acid amide, benzoic acid amide, tolu
Acid amides such as ylamide, methylamine, ethylamine, diethylamine, trib
Thylamine, Piperidine, Tribenzylamine, Anili
pyridine, picoline, tetramethylenediamine, etc.
amines; acetonitrile, benzonitrile, tolnitrile, etc.
Nitriles: etc. can be exemplified. These electron donors are one type
Can be used alone or in combination of two or more
can. Among these, organic acid esters, especially aromatic
Preferably, aromatic carboxylic acid esters are used. Matako
These electron donors do not necessarily have to be used as starting materials.
[A] It is produced in the process of preparing the solid titanium catalyst component.
You can also make it happen. Also, these can be combined with other compounds.
It can also be used in the form of addition compounds or complex compounds. The solid titanium catalyst component [A] as described above is (a)
(i) Magnesium compound without reducing ability in liquid state
(ii) a titanium compound in a liquid state;
) in the presence of an electron donor that does not have active hydrogen.
It can be obtained by touching it. Further, the solid titanium catalyst component [A] is (b) the above (i)
) and 01), and then the above (iiD).
It can also be obtained by In the former aspect (a), in (1) above and/or
When (ii) contains an electron donor,
During the above contact, add a new electron donor (iii)
Although not necessary, electron donor 011) can be used in (i) and/or
or 0i) in advance, and then add (iii).
A method of making two contacts can also be adopted. The electron donor 011) is converted into a liquid magnesium compound (
i), a solution of the magnesium compound may contain
For those who have already described how to mix the magnesium compound solution into
When manufacturing by this method, it is added to the material to be dissolved in advance.
The following methods can be adopted. For example, an alkylmagnesium compound with reducing ability
The hydrocarbon solution contains no excess active hydrogen.
Those whose reducing ability has been eliminated by adding a child donor, or
Electron donor and active hydrogen with active hydrogen in hydrocarbon solution
The reduction ability is reduced by adding a mixture with an electron donor that does not have
Solubilize the solution in a hydrocarbon solvent using the method described above, and
You can also use this. Also, as an electron donor 0u)
is not itself an electron donor, but under certain conditions it can
Addition of a compound that can be converted into a child donor to react in situ.
Electron donor (iii) can also be generated by reaction.
Wear. The amount of electron donor (iii) used is the magnesium compound
0.01 to 10 mol, preferably 0.01 per mol
used in amounts of ~1 mol, particularly preferably 0.1-0.5 mol.
I can stay. Even when large amounts of electron donors are used, titanium compounds
By adjusting the amount used, a high-performance solid catalyst component can be obtained.
However, it is preferable to adopt the conditions described above.
. Titanium compounds in liquid state (under contact conditions) themselves
Liquid titanium compounds or hydrocarbon solutions of titanium compounds
It is. At this time, the electron donor 011) or the reaction
A compound that can be converted into an electron donor 011) in a liquid state is
It may be used by being included in a tan compound. However, that
does not form a complex with the electron donor 0u)
Large amounts of titanium compounds such that free titanium compounds are present
It is preferable to use That is, the electron donor (
iii) More than 1 mol of titanium compound per 1 mol
It is preferable to use it in an amount of 5 moles or more. The amount of titanium compound to be used is determined in addition to the above-mentioned contact operation.
Sufficient to form a solid without undergoing precipitation operations
If the amount is too small, the connection between the two
It is not possible to obtain the solid catalyst component as a precipitate by contacting the catalyst.
do not have. The amount of titanium compound used depends on its type, contact conditions, and
Although it varies depending on the amount of electron donor and other materials used,
About 1 mol or more, usually about 5 to 1 mol per 1 mol of lithium compound
About 200 mol, preferably about 10 to about 100 mol
is desirable. In addition, the titanium compound has an electron donor Qii
) About 1 mol or more, preferably about 5 mol per 1 mol
It is preferable to use the above ratio. In preparing the catalyst, (i) a catalyst having reducing ability in a liquid state;
(11) Titanium in liquid state
As an embodiment of contacting with the compound, the above-mentioned magnesium
Any compound that mixes the titanium compound in liquid state
method can be adopted. At this time, the shape and size of the solid catalyst component may vary depending on the contact conditions.
etc. may differ. A preferred method is to use liquid
titanium compounds in the state and magnesium compounds in the liquid state.
, their contact does not rapidly produce a solid product.
Mix the two at a sufficiently low temperature and then raise the temperature.
It is a method that gradually produces a solid product. to this method
According to granular or spherical solid catalyst with relatively large particle size
Ingredients are easy to obtain. Furthermore, in this method, Qii)
In the presence of an appropriate amount of an electron donor that does not have hydrogen,
- Granular or spherical solid catalyst with good bed granule distribution
A medium component is obtained. Polymers obtained using such catalysts
is granular or spherical, has a large particle size distribution and bulk density, and has a low flowability.
Good mobility. Note that granular here refers to expanded
Even if you look at the large photo, it looks like a collection of fine powder.
Refers to particles that form particles, and is used in the manufacturing method of solid catalyst components.
Therefore, the granular material has many irregularities on its surface.
It is possible to obtain something close to a true sphere. In the above contact, the contact temperature can be set appropriately.
However, this contact temperature wave is usually about -70 to +200℃.
The temperature is set within a range of degrees. should be contacted here
The temperatures of both liquids may be different. Generally, the above
It has a preferable granular or spherical shape and high
In order to obtain a solid catalyst component with high performance, as mentioned above, a mixture of the two is required.
It is preferable to use a method that does not use too high a temperature.
For example, under temperature conditions of -70 to +50℃
preferred. In this case, if the contact temperature is low, the solid material
There may be cases where no quality precipitation is observed, in which case
For example, the reaction may occur by raising the temperature to about 50 to 150℃, or
It is best to precipitate the solid product by prolonged contact.
stomach. The solid product preferably comprises a liquid titanium compound,
More preferably, the excess titanium tetrachloride is about 50 to about 1
Preferably, one or more washes are carried out at a temperature of 50°C. the
Afterwards, it can be used for polymerization, usually after washing with a hydrocarbon. This method involves combining a high-performance solid catalyst component with a relatively simple operation.
There is an advantage that can be obtained by making a product. In addition, in the above-mentioned embodiment (b),
The catalyst can be prepared using Monomagnesium compound in liquid state and titanization in liquid state
and the compound in the same proportions as in the method in embodiment (a) and
A suspension containing the solid product is obtained. Generally, an electron donor (iii) is added to this suspension;
For example, a method of reacting at a temperature of about 0 to 150°C is adopted.
used. The amount of electron donor used is in the embodiment (a)
Same as in case. Also, the above aspects (a) and (b) can be used together.
Wear. According to this combination method, according to the aspect (a), the particle size
Fine adjustment of catalyst preparation is possible by adjusting the shape and shape of the catalyst.
It is possible to perform adjustments. Examples of combination use include:
Magnesium in liquid state in the coexistence of electron donor 011)
contacting the compound with a titanium compound in a liquid state, and
The process of depositing a solid product and the electron
Mention methods for adding and contacting donor 011)
I can do it. Solid titanium catalyst component obtained by each of the above embodiments [
A] must be thoroughly washed with hydrocarbon before being subjected to polymerization.
is preferred. The composition of the solid titanium catalyst component [A] thus obtained is
, Magnesium/Titanium (atomic ratio) is usually about 2-100
1 Preferably about 4 to 50, more preferably about
5 to about 30, and the halogen/titanium (atomic ratio) is usually about 4 to 100, preferably
preferably about 5 to 90, more preferably about 8 to about 5
0, and the electron donor/titanium (molar ratio) is usually about 0.01 to 10
0, preferably about 0.2 to about 10, more preferably
is about 0.4 to about 6. In addition, as already mentioned, in many cases the shape is granular or
Or almost spherical. Also, its specific surface area is usually
About 10y/g or more, preferably about 100-1000rf
/g. Next, the organometallic compound catalyst component [B] will be explained. Organometallic compound catalyst component of Groups 1 to M of the periodic table [B
], at least one AQ-carbon bond in the molecule
Compounds having the following are available. As such compounds
For example, (1) Formula R1-At) (OR2). H,X. (In the formula, R1 and R2 are each independently a carbon atom
A hydrocarbon group containing usually 1 to 15, preferably 1 to 4
It is. X represents a halogen atom, 0<m≦3, n is
0≦n<3, p is 0≦p<3, q is a number O≦q<3
Moreover, m+n+p+q=3)
Organoaluminum compound; (2) MIAiR14 (in the formula, M is Ll, Na, and R1 is the same as above)
A complex aluminium of group II metal and aluminum represented by
Examples include killed compounds. In addition to these aluminum compounds, for example, (3) RIR2M2 (wherein R1 and R2 are the same as above, and M2 is M
g, Zn, and Cd. ) Group ■ represented by
Metal dialkyl compounds: etc. As organoaluminum compounds belonging to (1) above,
, the following compounds can be exemplified. Formula R', Af (OR2) s- (wherein R1 and R2 are the same as above. m is preferably
1.5≦m≦3), formula R1-A QX, -. (In the formula, R1 is the same as above. X is halogen, m is preferably
and O<m<3), formula R1, A t H, -. (In the formula, R1 is the same as above. m is preferably 2≦m<3
), formula R1゜AR(OR2) , ,X. (In the formula, R1 and R2 are the same as above. X is halogen,
O<m≦3.0≦n<3.0≦q3, m + n
10q = 3)
be able to. As aluminum compounds belonging to (1), more specifically
Specifically, triethylaluminum, tributylaluminum
Trialkenyl aluminum such as nitriisoprenylaluminium
Luminium. Diethyl aluminum ethoxide, dibutyl aluminum
Dialkyl aluminum alkoxy such as mubutoxide
Do: Ethylaluminum sesquiethoxide, butylaluminum
Alkyl aluminum sesces such as umsesquibutoxide
Chialkoxide, R'2. AQ (OR2). , the average expressed as , etc.
A partially alkoxylated alkyl alkyl having the composition
Minium diethylaluminum chloride, dibutylaluminum
dials such as chloride, diethylaluminum bromide, etc.
Kill aluminum halide; ethyl aluminum sesqui
Chloride, butylaluminum sesquichloride, ethyl
Alkyl aluminum such as aluminum sesquipromide
Museski halide. Ethylaluminum dichloride, propylaluminum
Aluminum dichloride, butylaluminum dibromide, etc.
Partially halogenated such as kill aluminum cybaride
Alkyl aluminum: diethyl aluminum hydride, dibutyl aluminum
Dialkyl aluminum hydride such as hydride: ethyl aluminum dicdride, probyl aluminum
Alkylaluminum dihydrides such as dihydrides, etc.
Other partially hydrogenated alkyl aluminum; ethyl aluminum ethoxy chloride, butyl aluminum
Umbutoxy chloride, ethylaluminum ethoxyp
Partially alkoxylated and halogenated compounds such as lomids
Examples include aluminum alkyls. In addition, compounds similar to (1) include oxygen atoms and nitrogen atoms.
Organic aluminum in which two or more aluminum atoms are bonded through atoms
Examples include minium compounds. Such a compound
For example, (C2H5)2AQ OAR (C
zH5)2, (C, He) 2. Al10AQ (C4
Ha)2, (CzHs), AQNAG (C2Hs)
2. Ru. Compounds belonging to the above (2) include LiA Q (C2H3) 4, LiA R (C7H
15) 4 etc. can be mentioned. Among these, especially trialkyl aluminum or
is an aluminum compound in which two or more of the above aluminum compounds are combined.
Preferably, aluminum aluminium is used. In addition, as a compound belonging to the above (3), diethylzinc
, diethylmagnesium, etc. Also alkylmagnesium such as ethylmagnesium chloride
Nesium halide can also be used. Among the above (1), (2), and (3), especially
alkyl aluminum, alkyl aluminum halide,
Alternatively, it is preferable to use a mixture thereof. An olefin containing the above-mentioned [A] acid component and [B] acid component.
Olefin polymerization using a fin polymerization catalyst is ethylene
Copolymerization is not limited to copolymerization between
Small amounts of other a-oles other than ethylene and pentene-1
Fins or polyenes are present in the reaction system, and the three components are
It is also possible to copolymerize more or more components. Ethylene/pentene-1 copolymer [I] used in the present invention
is carried out by the gas phase polymerization method described below using the above catalyst.
It can be manufactured as follows. For gas phase polymerization, a method using a fluidized tank or an agitated fluidized tank is used, and the solid titanium catalyst component [A] may be used in solid form or
or suspended in a hydrocarbon medium or olefin, etc.
The organometallic compound catalyst component [B] is diluted or not diluted.
It is directly fed into the polymerization system. Furthermore, by supplying hydrogen into the polymerization system, the polymer can be separated.
The molecular weight can be controlled. In the above production method, it is preferable to use a prepolymerized catalyst.
stomach. - For prepolymerization, the catalyst component [A], the above organic
In addition to the metal compound [B], the above as an outside donor
An electron donor catalyst component can also be present. that time
The content of the titanium catalyst component [A] is 0.00% per gram of titanium.
01 to 30 mol, preferably 0.1 to 10 mol, more preferably
Preferably, the electron donor catalyst component is in the range of 0.5 to 5 mol.
You can also use Prepolymerization can also be carried out in an inert hydrocarbon solvent or in a liquid monomer.
Number of carbon atoms with or without solvent
Prepolymerize 2 to 10 a-olefins, but inert
Prepolymerization in a hydrocarbon solvent is more preferred. The polymerization amount in the prepolymerization is 0.00% per 1g of titanium catalyst component.
5-5000g, preferably 1-1000g, more preferably
Preferably, it is 3 to 200 g. The inert hydrocarbon solvent used in prepolymerization is
Lopane, butane, n-pentane, isopentane, n-he
xane, isohexane, n-hebutane, n-octane,
isooctane, n-decane, n-dodecane, kerosene, etc.
Aliphatic hydrocarbons, cyclopentane, methylcyclopenta
Fats such as cyclohexane, cyclohexane, and methylcyclohexane
Cyclic hydrocarbons, such as benzene, toluene, and xylene
aromatic hydrocarbons, methylene chloride, ethyl chloride
, ethylene chloride, halogens such as chlorobenzene
Examples include carbonized hydrocarbons, among which aliphatic carbons
Hydrocarbons, especially aliphatic hydrocarbons having 3 to 10 carbon atoms
preferable. Use of inert solvents or liquid monomers in prepolymerization
When using titanium catalyst component [A] per solvent IQ,
0.001 to 500 mmol in terms of ion atoms, especially
o, oos to 200 mmol, or
AQ/Ti (atomic
ratio) is 0.5 to 500, preferably 1.0 to 50, and
It is preferably used in a ratio of 2.0 to 20.
is preferred. As the a-olefin used for prepolymerization, ethylene
propylene, butene-1, pentene-1,4-methylene
Lupentene-1,3-methylpentene-1, heptene-
1, octene-1, ace-1 and carbon atoms of 10 or less
Ethylene is particularly preferred. child
These σ-olefins may be homopolymerized or crystalline polymers.
Copolymerization of two or more types is acceptable as long as a polymer is produced.
stomach. The polymerization temperature in prepolymerization depends on the a-olefin used.
It also varies depending on the type of inert hydrocarbon solvent.
Although it cannot be generally specified, it is generally -40 to 80°C, preferably
-20~40℃, more preferably -10~30℃
It is a warehouse. Hydrogen can be present in the prepolymerization. In the above production method, preferably the prepolymerized
Copolymerization of ethylene and pentene-1 using the catalyst described above (this paper)
polymerization). In the main polymerization, the a-olefin is prepolymerized.
1 per gram of titanium catalyst component [A] of the combined catalyst
．． 000-100.000g, preferably 2.000g
~50.000g, more preferably 3.000~
30,000 g of ethylene-pentene-1 copolymer (A
) is manufactured. per gram atom of titanium in the titanium catalyst component [A]
1 to 1000 mol of organometallic compound catalyst [B], preferably
preferably 3 to 500 mol, particularly preferably 5 to 100 mol
Preferred for use. Also, other compounds such as electron donating
A catalyst component may be added, in which case the organometallic
10 per gram atom of metal element in compound catalyst component [B]
0 mol or less, preferably 1 mol or less, particularly preferably 0.
It is preferred to use between 0.001 and 0.1 mol. Polymerization temperature is 20-130°C, preferably 50-120°C
, more preferably at 70 to 110°C. The polymerization pressure is 1
~50kg/cm2, preferably 2-30kg/cm2
More preferably, it is 5 to 20 kg/cm2. Also
, methane, ethane, propane, butane, nitrogen, etc. polymerization systems
An inert gas which forms a gaseous state within the chamber may be supplied as appropriate.
stomach. The above polymerization can be carried out by batch, semi-continuous or continuous method.
It can also be done in Ethylene-pentene-1 copolymer constituting the composition of the present invention
As for coalescence, ethylene obtained by the above production method is used.
・Pentene-1 copolymer [r] can be used
However, along with this ethylene-pentene-1 copolymer [+]
, or alternatively an ethylene pen as described below.
Ten-1 copolymer [+]] and/or ethylene
Tenten-1 copolymer [[+1] can also be used
. This ethylene/pentene-1 copolymer [■co, and [m
] is a copolymer with a specific DSC peak pattern.
be. That is, generally using an ethylene-pentene-1 copolymer,
, After heating up to 200℃ and melting, lower the temperature by 10℃/min.
A 0.5 mm thick sample obtained by cooling and crystallizing at a high speed.
Create a pull sheet and DS about this sample sheet
Using C at a heating rate of 10°C/min from 10°C
DSC melting peak pattern obtained when heating up to 200℃
The turn shows three peaks (see Figure 2). On the other hand, by adjusting the preparation conditions, ethylene
The temperature of the pentene-1 copolymer was raised to 200℃ and melted.
After that, the temperature was lowered to 50℃ at a cooling rate of 0.31℃/min.
A sheet with a thickness of 0.5 mm obtained by slow cooling and crystallization (
Below, the samples obtained in this way are
Create a sample sheet (called "Pull") and use this sample
10℃/m from 10℃ using DSC
Obtained when the temperature is raised to 200℃ at a heating rate of in.
The DSC melting peak pattern has two melting peaks,
The high temperature side peak height Hh and the low temperature side peak height HQ
The ratio Hh/He and the density d of the copolymer satisfy the following formula:
(See Figure 1). 0 <Hh/He < 80d -69,0 Set of the present invention
Ethylene/pentene-1 copolymer that constitutes the product [■]
is ethylene pentene with SC characteristics as described above.
The Hh/He value of the 1-1 copolymer satisfies the following formula:
It is a copolymer. 60d -52,0<Hh/HQ<80d -69
,0...[5] Ethylene having SC characteristics as shown below
Pentene-1 copolymer [II] is a so-called “gas phase polymer”.
It can be manufactured by "combination". Ethylene/pentene-1 copolymer [ml is as above
Ethylene/pentene-1 copolymer with SC properties
A copolymer whose Hh/H1l value satisfies the following formula:
be. 0 <Hh/HQ < 60d -52,0 like this
Ethylene/pentene-1 copolymer with SC properties [
ml can be produced by so-called "solution polymerization".
Ru. The following is an ethylene/pentene-1 copolymer [details about nl]
A detailed explanation will be given, and then ethylene/pentene-1 copolymer [
ml will be explained in detail. MFR of this ethylene-pentene-1 copolymer [lI]
, density, content of repeating units derived from pentene-1
Regarding the percentage and RS, the above-mentioned ethylene pentene
-1 copolymer (A). However, the density of ethylene/pentene-1 copolymer [nl
The width is within the range of ethylene/pentene-1 copolymer (A)
It tends to be somewhat narrower than that, preferably from 0.88 to
0.95g/cm3, particularly preferably 0.89-0.
It is within the range of 941/cm3. In addition, ethylene/pentene-1 copolymer [in nl
The content of repeating units derived from pentene-1 is
It is desirable that it be somewhat higher, preferably 2 in monomer terms.
~25% by weight, more preferably 4-23% by weight, especially
Preferably it is within the range of 6 to 20% by weight. Along with this
Therefore, the content of repeating units derived from ethylene is
Usually 75 to 98% by weight, preferably 7% by weight in terms of monomer
7 to 96% by weight, particularly preferably 80 to 94% by weight.
It is within the surrounding area. This ethylene-pentene-1 copolymer [■] Nemo, the above
Other a similar to ethylene/pentene-1 copolymer [■]
-Olefins or polyenes are copolymerized.
Good too. This ethylene/pentene-1 copolymer [nl is the above
DSC of "ultra slow cooling sample"
The value of Hh/HQ measured from the melting peak pattern
The copolymer [nl density d satisfies the following formula [5]. 60d -52,0<Hh/HI! < 80d -69
,0...[5] Furthermore, the relationship between the value of Hh/HQ and the density
It is preferable that the relationship has the following formula [5°], and further,
It is particularly preferable that
. 60d -52,0<Hh/H (1< 80d -69
,1...[5゛]60d -51,9<Hh/HQ
< 80d -69,2...[5"] However, in the above formula
where Hh is the peak height on the high temperature side and He is the peak height on the low temperature side.
The height and d represent the density of the copolymer. Ethylene-pentene-1 copolymer with such characteristics
body [nl is ethylene and pentene-1 under specific conditions
Co-polymerized in the presence of a catalyst for olefin polymerization as described below.
It can be produced by polymerization. When producing ethylene/pentene-1 copolymer [nl
Examples of the olefin polymerization catalyst used include (A1) a mixture containing a magnesium compound and an electron donor;
Magnesium compounds in liquid state formed from compounds or
is formed from a solution of a magnesium compound in a hydrocarbon solvent.
RIO group obtained from liquid magnesium compound
and R2 group (R1 and R2 are each a hydrocarbon group)
solid magnesium-aluminum composite, (A2) a mixture containing a magnesium compound and an electron donor;
Magnesium compounds in liquid state formed from compounds or
is formed from a solution of a magnesium compound in a hydrocarbon solvent.
RIO group obtained from liquid magnesium compound
or RIOH-containing OH magnesium compound (B) or
or any of the above (A,) and groups Ⅰ to m of the periodic table.
By reacting a group metal with an organometallic compound (C)
R10 group and Rs group (RS is a hydrocarbon group) obtained by
) Containing solid magnesium-aluminum composite, containing a hydrocarbon compound selected from (A, ) or (A2) above.
Solid magnesium-aluminum complex and tetravalent
A small amount obtained by reacting with a titanium compound.
At least 10% or more of titanium atoms in a low valence state
Contains an OR group of 1 to 15 in OR/Mg (weight ratio)
Solid titanium catalyst component for olefin polymerization [A
] and an organoaluminum compound catalyst component [B]
Examples include catalysts for fin polymerization. This olefin polymerization catalyst and the use of this catalyst will be explained below.
I will explain the reaction system in which ethylene/pentene
1 Copolymer [n] can be used only in these catalyst systems or reaction systems.
However, it can also be produced using other catalyst systems or reaction systems.
be. The above [A] solid titanium catalyst component for olefin polymerization is
, typically starting from a liquid magnesium compound.
The organoaluminum compound and the RIO group (Rt is carbonized)
Hydrogen group) forming compound and optionally add other reaction reagents.
RIO group and hydrocarbon obtained by using together and reacting with each other
A magnesium-aluminum complex with a group and a tetravalent
Low valence titanium obtained by reacting with titanium compounds
It is a supported component. Magnesium compounds in liquid state are, for example, magnesium
Hydrocarbons, electron donors, or a mixture of these
It may be dissolved in a substance, and a solution of a magnesium compound may be used.
It may be a melt. Magnesium used for this purpose
Magnesium chloride, magnesium bromide,
halogens such as magnesium, magnesium iodide, and magnesium fluoride.
Magnesium genide; methoxymagnesium chloride, etho
Magnesium oxychloride, isopropoxymagnesium chloride
Magnesium butoxychloride, Magnesium octoxychloride
Alkoxymagnesium halide such as sium: Fe
magnesium oxychloride, methylphenoxymagnesium chloride
Allyloxymagnesium halide such as sium; etho
xymagnesium, impropoxymagnesium, buto
Acids like oxymagnesium, octoxymagnesium
Lukoxymagnesium: phenoxymagnesium, dime
Allyloxymagnesium like tylphenoxymagnesium
Cium; Magnesium laurate, Magnesium stearate
Examples of carboxylates of magnesium such as sium
can do. In addition, the magnesium compound is
Complex compounds with metals, composite compounds or other metal compounds
It may be a mixture of. Additionally, two of these compounds
It may be a mixture of the above. Among these, preferred magnesium compounds are Mgx2
, Mg(OR')X , Mg(OR')2 (however
X is halogen, RS is a hydrocarbon group)
magnesium chloride, alkoxymagnesium halide,
Ryloxymagnesium halide, alkoxymagnesium
aryloxymagnesium, preferably halogen.
Magnesium compounds containing magnesium, especially magnesium chloride
, alkoxymagnesium chloride, allyloxymagnesium chloride
magnesium, particularly preferably magnesium chloride
. These magnesium compounds in liquid state include
Gnesium compounds are soluble in hydrocarbon solvents and electron donors.
or a mixture thereof is suitable. child
Hydrocarbon solvents used for this purpose include pentane,
Hexane, heptane, octane, decane, dodecane,
Aliphatic hydrocarbons such as tetradecane and kerosene; cyclope
cyclopentane, cyclopentane, cyclohexane, methi
cyclohexane, cyclooctane, cyclohexene
Alicyclic hydrocarbons such as benzene, toluene, xylene
Aromatic carbons such as carbon, ethylbenzene, cumene, and cymene
Hydrogenides, dichloroethane, dichloropropane, trichloride
Halides such as chlorethylene, carbon tetrachloride, and chlorobenzene.
Examples include logenated hydrocarbons. To obtain magnesium compounds dissolved in hydrocarbon solvents
, depending on the type of compound and solvent used.
, a method of simply mixing both (for example, carbon source as RS)
method using Mg (OR') 2 with a child number of 6 to 20),
The method of mixing and heating the soluble magnesium compound
Electron donors, e.g. alcohols, aldehydes, amino acids
carboxylic acids, any mixture thereof, as well as
and other electron donors, etc., as necessary.
Depending on the temperature, a heating method can be adopted. parable
For example, if a halogen-containing magnesium compound is mixed with alcohol,
Regarding the case of dissolving in a hydrocarbon solvent,
Type and amount of hydrocarbon solvent used, species of magnesium compound
Although it varies depending on the type, alcohol is preferably
Approximately 1 mol per 1 mol of halogen-containing magnesium compound
The above, preferably about 1 to about 20 mol, particularly preferably about 1 mol
．． It is used in a range of 5 to about 12 moles. as a hydrocarbon
Using aliphatic and/or alicyclic hydrocarbons
If alcohol is used in the above proportions,
Alcohols with 6 or more carbon atoms are mixed with halogen-containing materials.
Approximately 1 mol or more per 1 mol of the gnesium compound, preferably
If about 1.5 mol or more is used, the total amount of alcohol used will also be reduced.
It is possible to solubilize halogen-containing magnesium compounds in a small amount.
and is preferable because it becomes a catalyst component with a good shape.
. In this case, for example, an alcohol having 5 or less carbon atoms may be used.
1 mole of halogen-containing magnesium compound
However, approximately 15 moles or more of alcohol is required.
The medium shape is also not as good as the above system. On the other hand, aromatic as a hydrocarbon
If group hydrocarbons are used, regardless of the type of alcohol.
, halogen-containing magnets with the amount of alcohol used above.
Solubilization of sia compounds is possible. Contact of halogen-containing magnesium compounds with alcohol
is preferably carried out in a hydrocarbon medium, usually at room temperature or below.
Above, depending on the type, the temperature is about 65°C or higher, preferably about 65°C or more.
80 to 300°C, preferably about 100 to about 200°C
About 15 minutes to 5 hours at temperature, more preferably 30 minutes to 2 hours.
This is done by making contact for a while. Suitable alcohols are those having 6 or more carbon atoms.
For example, 2-methylpentanol, 2-
Ethylbutanol, n-heptatool, n-octatool
2-ethylhexanol, decanol, dodecano
alcohol, tetradecyl alcohol, undecenol, ole
Aliphatics such as yl alcohol and stearyl alcohol
Alcohol, cyclohexanol, methylcyclohexane
Alicyclic alcohols such as nol, benzyl alcohol
, methylbenzyl alcohol, isopropylbenzyl alcohol
alcohol, a-methylbenzyl alcohol, σ, α-di
Aromatic alcohols such as methylbenzyl alcohol, n
-Butyl cellosolve, 1-butoxy-2-propatol
Examples include aliphatic alcohols containing alkoxy groups such as
can be shown. Examples of other alcohols include methanol,
Tanol, propatool, butanol, ethylene glyco
carbon atoms such as alcohol, methylcarpitol, etc.
Lecole can be mentioned. Electrons other than alcohol as a solution of magnesium compounds
Solutions of the donor can also be used. For purposes like this
Preferred examples of electron donors used are amines, alde
hydride and carboxylic acid. Examples of other electron donors are
Phenols, ketones, esters, ethers, amides, acids
With anhydrides, acid halides, nitriles, isocyanates, etc.
be. Quantitative relationships and melting temperatures when manufacturing these solutions
is generally dissolved in a hydrocarbon solvent using an electron donor.
Depending on the situation, it is necessary to maintain a high temperature numerically.
Therefore, from the perspective of catalyst preparation, it is necessary to prepare a catalyst dissolved in hydrocarbons.
It is easier to obtain high performance using . Other examples of liquid magnesium compounds are magnesium
It is a melt of compounds, such as magnesium halides.
and an electron donor, such as those exemplified above.
A representative example is a melt. The preferred one is
MgX2・nRIOH (R1 is a hydrocarbon group, n is a positive number)
The magnesium halide/alcohol complex shown in
It is a molten material. Next, from the liquid magnesium compound, the RIO group and
Solid magnesium with RS group (or R2 group)
Aluminum complex (R1, R2, RS are hydrocarbon groups
Therefore, Rs (or R2) is directly magnesium or
(reducing group bonded to aluminum)
This section describes how to do this. Magnesium aluminum here
The complex has the empirical formula, Mg, AQbR2° (or
R'e) (ORS) aX2゜ (X2 is halogen, 2a+
3 b = c + d + e), and in some cases other expressions
A compound or an electron donor may be further bonded. preferred
AQ/Mg (atomic ratio) is preferably 0.05 to 1, -layer
preferably 0.08 to 0.5, more preferably 0.12 to 0
．． 3. The RIO group is preferably per 1 part by weight of magnesium.
preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight
part, more preferably 2 to 6 parts by weight, hydrocarbon group R2 (
or Rs) is 1 part by weight of magnesium, preferably
0.01-0.5 equivalent, preferably 0.03-0.
3 equivalents, more preferably 0.05-0.2 equivalents, or
X”/Mg (JJil ratio) is preferably 1 to 3, -layer ratio
Preferably it is 1.5 to 2.5. Next, the magnesium-aluminum composite is manufactured.
A specific example will be described. Specific method for manufacturing magnesium-aluminum composite
The method uses a liquid magnesium compound and an organic alkali.
Method for directly producing composites by contacting minium compounds
can be mentioned. Magnesium compounds and organoaluminum compounds in liquid state
A compound having an RIO group in at least one of the compounds
or RIO-based acid-generating compounds such as RIOH groups.
It is also necessary to use a halogen compound. For example MgX2 and alcohol, preferably further
Solutions containing hydrocarbons and alkyl aluminum compounds
reaction, or Mg(ORS)X or Mg(OR'
) 2 and an alcohol, preferably further containing a hydrocarbon.
solution or a hydrocarbon solution of Mg(ORs)2.
can be obtained by reaction of rukylaluminum halide
can. Specifically, the alkyl aluminum compound mentioned above is
Triethyl aluminum, tributyl aluminum, etc.
trialkyl aluminum, triisoprenyl aluminum
trialkenylaluminum, diethyl
Aluminum ethoxide, dibutyl aluminum butoxide
Dialkyl aluminum alkoxides such as sido, ethyl
aluminum sesquiethoxide, butyl aluminum
Alkyl aluminum sesquia such as sesquibutoxide
Besides R1, AP (OR2). , the average expressed as , etc.
A partially alkoxylated alkyl alkyl having the composition
aluminum, diethylaluminum chloride, dibutylaluminium
Luminium chloride, diethylaluminium bromide
Dialkyl aluminum halide, such as ethyl aluminum
nium sesquichloride, butylaluminum sesquichloride
Lido, alkaline compounds such as ethylaluminum sesquipromide
Kill aluminum sesquihalide, ethyl aluminum
dichloride, propylaluminum dichloride, butyl
Alkyl aluminum such as aluminum dibromide etc.
Partially halogenated alkyls such as umushibalide
aluminum, diethylaluminum hydride, jib
Dialkyl aluminum such as chillaluminum hydride
Muhydride, Ethylaluminum Dicdride, Provil
Alkyl aluminum halide such as aluminum dihydride
Partially hydrogenated alkyl aluminum such as ladolide
um, ethyl aluminum ethoxy chloride, butyl aluminium
Luminium butoxy chloride, ethyl aluminum ethane
Partially alkoxylated and halogenated materials such as xypromide
It is a converted alkyl aluminum. In addition, as the alkyl aluminum halide, the above-mentioned examples include
selected from halogen-containing alkyl aluminum compounds.
can run. Liquid magnesium compound and alkyl aluminum compound
Not only the method of interacting with objects in one step, but also the liquid mag
Some alkylaluminum compounds of nesium compounds
to form a solid magnesium compound, and then
Then the same or the same as above is added to the solid magnesium compound.
is the case when different alkyl aluminum compounds are brought into contact.
It also includes multi-step contact such as Normally
The latter type of multi-step contact is better for magnesium.
It is easy to adjust the particle size of the compound, the amount of organic groups, etc., and it is highly
It is easy to obtain a high-performance catalyst. When performing such multi-step contact, the first step
After the completion of contact, the solid magnesium compound is separated from the liquid part.
and then proceed to the next reaction. Finally, in a solid magnesium-aluminum composite
It is preferable that the composition is within the above-mentioned range. this
For this purpose, the alkyl aluminum compound in the contact
It is preferable to use an appropriate amount of the material. For example, two stages
Regarding the method of contacting with an alkyl aluminum compound in
In other words, as a liquid magnesium compound, alcohol
When using a solution using alcohol, hydroxyl of alcohol
At least alkyl aluminum compound per equivalent of group
Used in a ratio such that the R2-Al2 bond of is 0.5 equivalent or more
It is preferable that On the other hand, alkyl aluminum compounds
If too much is used, the shape of the particles will deteriorate.
, granular catalyst may not be obtained. Therefore, usually
is the R2-A9 bond per equivalent of alcohol's hydroxyl group.
0.5 to 10 equivalents, preferably 0.7 to 5 equivalents, and
preferably 0.9 to 3 equivalents, particularly preferably 1.0 to 3 equivalents
It is preferable to use it within a range of 2 equivalents. At this time, trial-alkylated aluminum alkyl compounds are used.
If aluminum is used, a catalyst with good shape can be obtained.
It is preferable because it is watery. Other preferred organoaluminum compounds
The product is dialkyl aluminum halide, dialkyl aluminum halide,
Luminium hydride, dialkyl aluminum alkoxy
Sid and others. Liquid magnesium compound and alkyl aluminum compound
In contact with substances, magnesium compounds in liquid substances
Concentration is 0.005-2 mol/Q1, especially 0.05-2 mol/Q1
It is preferable to set it to about 1 mol/Q. Precipitation of magnesium compounds can occur, for example, on alkyl aluminum
Insoluble by reacting with alcohol
This occurs due to the formation of magnesium compounds. If the magnesium compound is rapidly precipitated, the particle shape will change.
It is difficult to obtain particles with good shape, moderate particle size, and narrow particle size distribution.
It may not be suitable as a catalyst carrier for slurry polymerization.
There are some things that cannot be achieved. For this reason, the contact should be gentle.
It is preferable to precipitate the solid under suitable conditions.
contact temperature, the temperature of the alkyl aluminum compound during solid precipitation.
Consider the amount or speed of addition, concentration of each component, etc.
This is desirable. Liquid magnesium compounds and organic aluminum compounds
For the reasons mentioned above, the contact temperature is between -50 and 100℃.
temperature range from -30 to 50℃, and then from 0 to 20℃.
The reaction is carried out at a temperature range of 0°C, preferably 40 to 150°C.
Now is preferable. As already mentioned, solid magnesi
After forming the aluminum compound, further alkyl aluminum compound is formed.
The temperature when catalytically reacting the rubber compound is 0 to 250°C,
In particular, a temperature of 20 to 130°C is preferred. In any case, the contact and reaction conditions are
The RO group and R2 group of the aluminum-aluminum complex have already been described.
It is preferable that the complex is in the range of
The particle size is 1 μm or more, especially 5 μm or more and 100 μm or more.
Below, the particle size distribution is in the geometric standard deviation range of 1.0 to 2.0.
, and the particle shape is selected to have properties such as granules.
It is preferable to do so. Note that contact is not performed after forming a solid magnesium compound.
Compounds that can be used as substitutes for alkylaluminum compounds include
In addition, materials from Groups I to M of the periodic table other than aluminum
metal compounds such as alkyllithium, alkylmer
Uses magnesium halide, dialkylmagnesium, etc.
manufacturing magnesium-aluminum composite
I can do it. Manufacturing solid magnesium/aluminum composites, etc.
The method described above is based on the alkyl aluminum compound
Halogenating agents, e.g. chlorine, chloride, at any stage of use
Those who use hydrogen, silicon tetrachloride, or halogenated hydrocarbons
method, and also before use of the alkyl aluminum compound,
Another method is to use a halogenating agent after use. These methods use alkyl aluminum halides
This method is useful as an alternative method. Add a halogenating agent before using the alkyl aluminum compound.
The method used is to prepare R from a liquid magnesium compound.
10 groups or RIOH-containing OH solid magnesium compound
It is useful as a means to generate . And it takes solid
Magnesium compounds and alkylaluminum compounds
solid magnesium by reacting with
aluminum-aluminum composites can be produced. and
If MgX2, Mg(ORS)X, Mg(ORS)
2 etc. and an alcohol, preferably further containing a hydrocarbon.
reaction of a solution with a halogenating agent, or Mg(OR'
) By the reaction of the hydrocarbon solvent of 2 and the halogenating agent, the above
The solid magnesium compound described above can be produced. The solid magnesium compound has the empirical formula % (O≦q<2, n≧0), optionally containing other compound components.
May form complex compounds with In this method, magnesium, which is usually found in magnesium compounds, is
The equivalent amount of halogen is about 1 to 1000 equivalents per 1 atom of
The solid magnesium compound used in the above ratio and the
The reaction with the alkylaluminum compound is a multistep process as described above.
It can be carried out according to the method in the later stages of the manufacturing method. Other ways to obtain solid magnesium compounds as mentioned above
is the cooling assimilation of molten MgX2-, (OR'), e nR60H,
Preferably, it is cooled and solidified while being dispersed in a hydrocarbon medium.
This is a method to In any of the above methods, solid magnesium compound
As a substance, if the particle size is 1 μm or more, especially 5 μm or more, 10
0 μm or less, particle size distribution with geometric standard deviation of 1.0 to 2.0
, and select precipitation conditions to obtain a spherical or granular shape.
It is preferable to do so. In addition, the solid magnesium aliobtained as described above
Reducing group R2 or RS contained in the luminium complex
The content can be determined as follows. The internal volume of a closed system sufficiently purged with dry nitrogen 2
Solid magnesium aluminum in a 00ml flask
Approximately 0.5g of Nium complex was added, and approximately 25ml of
Add water dropwise to the tap under stirring. After about 20 minutes, inside the flask
Extract the gas phase and aqueous phase with a microsyringe,
Measuring alkane concentration by gas chromatography
Ru. Add the volumes of the gas phase and water phase to these concentration values.
After adding up the respective multipliers, add up the two to get the generated algae.
Determine the total amount of cans, and use this total amount value as the total amount of cans present in the complex.
of alkanes produced by the reaction of alkyl groups with water.
the amount of reducing groups present in the complex, taken as a total amount;
You can think about it. The thus obtained RIO group and reducing organic group
Ti/
Mg (atomic ratio) is less than 1, preferably 0.01 to 0.7
, especially the usage ratio of good ma L < Ha 0.04-0.5
A solid titanium compound is produced by contacting it with a tetravalent titanium compound.
prepare something At least a portion of the supported titanium is
It is in a state of low valence, for example reduced to trivalent.
. Tetravalent used in the preparation of solid titanium catalyst component [A]
There are various titanium compounds, but usually T i (OR)
a X4-a (R is a hydrocarbon group, X is a halogen atom, O≦g≦4)
Mention may be made of the tetravalent titanium compounds shown below. Yo
Specifically, tetrahalogens such as TiCff14, TiBr4, TiI4, etc.
Titanium rogenide; Ti(OCH,)CQs. Ti(OC2H2)Ct, Ti(On-C,H,)C20, Tf(QC2H,)Br, T1(0-iso-C,H,)Br, etc.
Rogenated alkoxytitanium. Dihalogenated dials such as Ti(OCH,)2ce2, Ti(OC2H5)2CQ2, Ti(On-C4H@)2CR2, Ti(OC2H5)2Br2
Coxytitanium; Ti (OCH,), Cx, Ti (QC, H%), Cff1. Monohalogenated thoria such as Ticon-c4He)ace, Ti(QC2H5)3Br
Rukoxytitanium; Ti(OCH,), Ti(QC,Hs)4, Ti(On-C4H,), Ti(0-1so-C4H,)4, Ti(0-2-
Tetraalkoxytitanium such as ethylhexyl) 4, etc.
can be exemplified. Among these, Tet
Titanium trihalide, alkoxytitanium trihalide
is preferred, especially trihalogenated alkoxytitanium
Preferable to use. Solid magnesium-aluminum composite and titanium compound
The catalytic reaction of the product is preferably carried out in a hydrocarbon medium.
. When it comes into contact with a titanium compound, it regenerates into the final solid titanium.
In the catalyst component, R70 group/Mg (R7 is a hydrocarbon group)
Weight ratio of 0.5 to 15, preferably 1 to 10, particularly preferred
Alternatively, conditions are selected that fall within the range of 2 to 6. child
Here, the R70 group is a solid magnesium/aluminum complex.
Those derived from RIO& during coalescence and those derived from titanium compounds
It is something to do. If the R70 group is less than the above range,
In tyrene copolymerization, slurry polymerization is poor and the resulting
The composition distribution of the copolymer is also not sufficiently narrow. Ma
If the number of Rho groups exceeds the above range, it may cause a decrease in activity.
tends to cause Adjusting the Rho group in the solid titanium catalyst component to the above range
The type of titanium compound, amount used, contact temperature, etc.
Just adjust it. The contact temperature of titanium compounds is usually 0~
The temperature is about 200°C, preferably about 20 to 100°C. In forming the solid product described above, porous inorganic
and/or organic compounds can coexist,
thereby depositing the solid product on the surface of these compounds.
You may also adopt the method of At this time, the porous compound is made of magnesium in a liquid state in advance.
Magnesium compound in liquid state by preliminary contact with the compound
Contact with a liquid titanium compound while containing
Can also be done. Examples of these porous compounds include silica,
Alumina, magnesia, polyolefin and these
Examples include products treated with halogen-containing compounds.
Wear. In addition, aluminum, which is an essential component of this catalyst,
Porous compounds containing aluminum, magnesium, RO groups, etc.
In case of
This may occur. The titanium catalyst component thus obtained contains Mg, A11. Ti, (OR)) ,,)(1゜(formula
Medium r, s, t, u, v>0, Xl is ha
rogen), optionally with other compounds, and
For example, it contains silicon compounds. Here Ti/Mg (atomic
ratio) is usually 0.01 to 0.5, preferably 0.02 to 0
．． 2. AQ/Mg (atomic ratio) is 0.05 to 1, preferably
preferably 0.08 to 0.5, particularly preferably 0.12 to 0.
3. XS/Mg (atomic ratio) is 1.5 to 3, preferably 2
~2.5, ORF/Mg (weight ratio) is 0.5~15, favorable
The specific surface area is preferably 1 to 10, particularly preferably 2 to 6.
is 50~1ooott/g, preferably 150~
It shows 500 go/g. And 10-100% of all T1
It has a lower valence than Ti4. Such a solid titanium catalyst component [A] is an organic aluminum
In combination with the catalyst component [B], the olefin heavy
It can be used if The organoaluminum compound catalyst component [B] is a solid
It can be used for the preparation of titanium catalyst components.
selected from the alkyl aluminum compounds exemplified above.
You can choose. Among these are trialkylaluminum, alkyl
Aluminum halide or mixtures of these are preferred.
Yes. Contains the solid [A] acid component and [B] as described above.
Olefin polymerization using an olefin polymerization catalyst is
Not only the copolymerization of lene and pentene-1, but also the copolymerization of ethyl
A small amount of other a-olefins other than lene and pentene-1
Alternatively, the polyene may be present in the reaction system, and the three components or
It is also possible to copolymerize more than 100% of the components, especially
Useful when copolymerizing ren and pentene-1 in the gas phase.
be. The polymerization reaction is carried out in the gas phase, and this reaction is carried out in a fluidized bed reactor, with stirring.
Using method reactors, stirred flow reactors, tubular reactors, etc.
It can be carried out. The solid titanium catalyst component [A] may be used in solid form or
or suspended in a hydrocarbon medium or olefin, etc.
The organoaluminum compound catalyst component [B] is diluted and
is fed into the polymerization system as is without dilution. Furthermore, by supplying hydrogen into the polymerization system, the polymer can be separated.
The molecular weight can be controlled. When adopting this production method, use of prepolymerized catalyst
is preferred. For prepolymerization, catalyst component [A], upper
In addition to the organoaluminum compound catalyst component [B], the above electrolyte
A child donor catalyst component can also be present. In that case, the applicable
0.0 per gram atom of titanium in titanium catalyst component [A]
1 to 30 mol, preferably 0.1 to 10 mol, more preferably
Alternatively, an electron donor catalyst component in the range of 0.5 to 5 moles may be used.
It can also be used. In addition, prepolymerization is performed using inert hydrocarbons.
in a solvent or with a liquid monomer as a solvent;
Reserve α-olefin with 2 to 10 carbon atoms without using
polymerization, but prepolymerization in an inert hydrocarbon solvent is preferred.
More preferable. The polymerization amount in the prepolymerization is 0.00% per 1g of titanium catalyst component.
5~sooog, preferably 1~1000g, more preferably
Preferably, it is 3 to 200 g. Examples of inert hydrocarbon solvents used for prepolymerization are
, propane, butane, n-pentane, isopentane, n
-hexane, isohexane, n-hebutane, n-octa
N, isooctane, n-decane, n-dodecane, kerosene, etc.
Which aliphatic hydrocarbons, cyclopentane, methylcyclope
cyclohexane, methylcyclohexane, etc.
alicyclic hydrocarbons, benzene, toluene, xylene,
Aromatic hydrocarbons such as methylene chloride, ethyl chloride
halo such as lido, ethylene chloride, chlorobenzene
Examples include hydrogenated hydrocarbons. Among these
But aliphatic hydrocarbons, especially fats with 3 to 10 carbon atoms,
Group hydrocarbons are preferred. Use of inert solvents or liquid monomers in prepolymerization
When using titanium catalyst component [A] per solvent IQ,
0.001 to 500 mmol in terms of atoms, especially 0
．． 005 to 200 mmol, and
The machine aluminum compound [B] is A9/T i (N
ratio) 75t0.5-500, preferably Ha1.0-5
0°, more preferably at a ratio of 2.0 to 2o.
It is preferable to use As the a-olefin used for prepolymerization, ethylene
propylene, butene-1, pentene-1,4-methylene
Lupentene-1,3 - Methylpentene-1, Heptene-
1, 10 or less carbon atoms, such as octene-1, decene-1, etc.
Ethylene is particularly preferred. child
These a-olefins may be homopolymerized, or two or more types
Copolymerization may also be used. The polymerization temperature in prepolymerization depends on the α-olefin used.
It also varies depending on the type of inert hydrocarbon solvent and the type of inert hydrocarbon solvent.
Although it cannot be determined, the temperature is generally -40 to 80°C, preferably -
20 to 40°C, more preferably about -10 to 30°C.
Ru. Hydrogen can be present in the prepolymerization. Prepolymerization can be carried out either batchwise or continuously.
However, when carrying out a large amount of prepolymerization, a continuous system is preferable.
Delicious. In the present invention, preferably the prepolymerized catalyst is
Copolymerization of pentene-1 with ethylene is carried out using Applicable
In introducing the prepolymerized catalyst to the gas phase polymerization reactor,
The prepolymerized catalyst can be supplied in powder form or as described above.
It is preferable to supply it by suspending it in a hydrocarbon medium. Especially professional
Bread, 1so-butane, n-butane, 1so-pentane
It is preferable to supply it by suspending it in a low boiling point medium such as. a
-Titanium catalyst component of the catalyst prepolymerized with olefin
[A] Usually 1.000 to 100. o
oog, preferably 2,000-50,000g1
More preferably 3.000 to 30.000 g of ethylene
- Copolymerize a pentene-1 copolymer. per gram atom of titanium in the titanium catalyst component [A]
1 to 1000 mol of organometallic compound catalyst [B], preferably
preferably 3 to 500 mol, particularly preferably 5 to 100 mol
Preferred for use. Also, other compounds such as electron donating
A catalyst component may be added, in which case the organometallic
10 per gram atom of metal element in compound catalyst component [B]
0 mol or less, preferably 1 mol or less, particularly preferably 0
．． It is preferred to use between 0.001 and 0.01 mol. Polymerization temperature is 20-130°C, preferably 50-120°C
, more preferably at 70 to 110°C. Polymerization pressure is 1
~50kg/cm2, preferably 2-30kg/cm2
More preferably, it is 5 to 20 kg/cm2. Also
, methane, ethane, propane, butane, nitrogen, etc. polymerization systems
An inert gas which forms a gaseous state within the chamber may be supplied as appropriate.
stomach. When carrying out a polymerization reaction, [A] per 1 g of reaction volume
The solid titanium catalyst component has a TiW content of 0.
00001 to about 1 mmol, preferably about 0.0001
Preferably, it is used in a proportion of from about 0.1 mmol. Next, ethylene/pentene-1 copolymer [specifically about ml]
Explain physically. This ethylene-pentene-1 copolymer [ml MFR,
Density, content of repeating units derived from pentene-1
In terms of rate and RS, the above-mentioned ethylene pentene
1 copolymer (A). However, the density of ethylene/pentene-1 copolymer [ml
The width is within the range of ethylene/pentene-1 copolymer (A)
It tends to be slightly narrower than 0.87 to 0.94g.
/cm3, preferably 0.88-0.93g/cm3
It is. This ethylene/pentene-1 copolymer [III] also has
Others similar to the above ethylene/pentene-1 copolymer [I]
copolymerized with a-olefin or polyene, etc.
You can stay there. This ethylene/pentene-1 copolymer [ml is the above
DSC of "ultra slow cooling sample"
The value of Hh/Hll measured from the melting peak pattern and
This copolymer [density d in ml satisfies the following formula [6]
. o<Hh/HR<5od-52,0・[6 additionally, H
The relationship between the value of h/HQ and the density has the following equation [6'].
It is preferable that the relationship is expressed by the following formula [6'']
It is particularly preferable that 0<Hh/Hp<40d-34,5,,,c510<H
h/HQ< 1...[6”]However
, in the above formula, Hh is the peak height on the high temperature side and HQ is the peak height on the low temperature side.
The peak height and d represent the density of the copolymer. Ethylene-pentene-1 copolymer with the above properties
Coalescence [ml is ethylene and pentene-1, e.g.
Copolymerized in the presence of olefin polymerization catalysts such as
It can be manufactured by When producing ethylene/pentene-1 copolymer [ml
The olefin polymerization catalyst used is, for example, [A] halogen-containing magnesium compound, oleyl alkali
Liquid titanium contact consisting of coal and titanium compounds
formed from a medium component and [B] a halogen-containing organoaluminum compound.
It is. As halogen-containing magnesium, magnesium chloride
, Magnesium Bromide, Magnesium Iodide, Magnesium Fluoride
Magnesium chloride is used, especially magnesium chloride.
is preferably used. Examples of titanium compounds include Ti(OR), X, □ (in the formula R
is a hydrocarbon group, X is a halogen, and g is O~4
A tetravalent titanium compound represented by the following is used. Specifically, as such a titanium compound, 'ri
Tetrahalogens such as cp, , TiBr4, TiI, etc.
Ti(OCR,)CQ, Ti(OC,H,)Cvs, T1(0-i C,H,)CI2s, Ti(0-n
C,H,)CI! 3, T 1 (OC2H5) B
Trihalogenation of Ti(0-i C,H,)Br, Ti(0-i C4H,)Br, etc.
Alkoxy titanium; Tt(OCH3), CR2, Ti(OC2H,)2CR2, Ti(0-i C,H,)2CQ2, Ti(On C
Dihalogenated alcohols such as 4Hg)2CQ2, Ti(OC2Hs)zBrz
Oxytitanium; Ti (OCHs) s CR'ri(OC2H,)3Cff1 Ti(0-i C,H7), CR Ti(0-n C,H,)sCQ Ti(○C2Hs)3Br Rogenicht
1-noalkoxy titanium. Ti(OCR,)4, Ti(OC2HsL, 'ri(0-nC,H,)4゜Ti(0-iC,H))4N Ti(0-n C4H11)41 Ti(OC6H13)4, Tt( OC6Htt) 4, T
i(OC6HI?)4, T 1 [OCH2(C2Hs) CHC4H* 1
4, Ti(OC9HI9)4, 'ricoc6Hs(CH3)2]4, Ti(OC
16Hss)4, Ti(OCH3)2(OC4H9)2, Ti(QC,
H7) g(QC<H*), Ti(OC2H5)-hCO
C4H,)t, Ti(QC2H,)z(0-i C3H
? )2,'ri(o C2H3)(OC1aHss)s
5Ti(OC2H5)2(OCsaHas)z, Ti
(OC1Hz)B(OC5aHss) and other tetraal
Examples include koxytitanium. Among these
Then, 1≦g≦4 is preferable, and 2≦g≦4 is more preferable.
In particular, tetraalkoxy titanium is preferably used.
. When producing ethylene/pentene-1 copolymer [ml
The [A] liquid titanium catalyst component used is the above-mentioned
Magnesium containing halogens such as oleyl alcohol
and a substantially homogeneous composition of titanium compounds as described above.
It is a solution. Such [A] titanium catalyst component in liquid state is
For example, halogen-containing magnesium and oleyl alcohol.
and then combine this mixture with a titanium compound.
It is preferable to make contact with an object. Halogen-containing magnet
A mixture of sium and oleyl alcohol is a solution
It can be in a state or a suspension state, but it can be in a solution state.
It is preferable that there be. Also, do not mix the three components and
Another preferred method is to change the state
. [A] When preparing a titanium catalyst component in a liquid state, 4
0°C or higher, preferably 40 to 200°C, more preferably
At 50-150℃, halogen-containing magnesium and oleay
a mixture consisting of alcohol and a titanium compound.
minutes or more, preferably 15 minutes to 24 hours, particularly preferably
It is desirable to react by contacting for 30 minutes to 15 hours.
stomach. [A] The titanium catalyst component in liquid state contains halogen.
Magnesium, oleyl alcohol and titanium compounds
and at the same time 40℃ or higher, preferably 40 to 200℃, and further
Preferably at 50-150°C for 1 minute or more, preferably
15 minutes to 24 hours, particularly preferably 30 minutes to 15 hours.
V) can also be prepared by contacting and reacting.
. Halogen-containing magnesium, titanium compounds and oleis
Preparation of liquid titanium catalyst component consisting of alcohol
In this case, a hydrocarbon solvent can also be used. In other words, halogen-containing magnesium and oxygen are added to a hydrocarbon solvent.
Dissolve the rail alcohol and then contact with the titanium compound.
It is also possible to add halogen-containing magnesium to the hydrocarbon solvent.
Dissolve titanium compound, oleyl alcohol and titanium compound.
They may be brought into contact with each other. Such hydrocarbon solvents include pentane, hexane,
, heptane, octane, decane, dodecane, tetradeca
Aliphatic hydrocarbons such as carbon, kerosene; cyclopentane, methane, etc.
cyclopentane, cyclohexane, methylcyclohexane
Alicyclic carbonization of San, cyclooctane, cyclohexene, etc.
Hydrogens: benzene, toluene, xylene, ethylbenze
Aromatic hydrocarbons such as chlorine, cumene, and cymene;
Tan, dichloropropane, trichlorethylene, tetrachloride
Carbon, halogenated hydrocarbons such as chlorobenzene, etc.
is used. Halogen-containing magnesium, titanium compounds and oleis
Alcohol is preferably used in the following amounts:
Delicious. Oleyl alcohol/MgCffi is usually a molar ratio
Z~4 is preferably 2-3. Titanium compound/MgC1)□ usually has a molar ratio of 0.04
-0.30 preferably 0.05-0.20. Oleyl alcohol/titanium compound has a molar ratio of 5 to 10
0, preferably 10-80. When producing ethylene/pentene-1 copolymer [m]
As the [B] halogen-containing organic aluminum used
is diethylaluminum chloride, dibutylaluminum
aluminum chloride, diethylaluminum bromide, etc.
Alkyl aluminum rhamno-1lide: ethyl aluminum sesquichloride, butyl aluminum
Musesquichloride, Ethylaluminum Sesquipromide
Alkylaluminum sesquihalides such as; ethylaluminum dichloride, propylaluminum
Aluminum dichloride, butylaluminum dibromide, etc.
Partially halogenated such as kill aluminum cybaride
Alkyl aluminum ethyl aluminum ethoxy chloride, butyl aluminum
Umbutoxy chloride, ethylaluminum ethoxyp
Partially alkoxylated and halogenated compounds such as lomids
Examples include aluminum alkyls. In addition to these halogen-containing organic A9 compounds, halogen
Organic AQ compounds that do not contain carbon can also be used, even if
For example, triethylaluminum, tributylaluminum, etc.
Which trialkylaluminum nitriisoprenylaluminum
Dry alkenyl aluminum such as aluminum. Diethyl aluminum ethoxide, dibutyl aluminum
Dialkyl aluminum alkoxy such as mubutoxide
Do. Ethyl aluminum sesquiethoxide, butyl aluminum
Alkyl aluminum sesces such as umsesquibutoxide
Chialkoxide, R'2.5Affi (OR2). expressed as 5 etc.
partially alkoxylated alkyl with an average composition of
Aluminum. Diethylaluminium hydride, dibutylaluminum
Dialkyl aluminum hydride such as hydride, ethyl aluminum dicdolide, probyl aluminum
Alkylaluminum dihydrides such as dihydrides, etc.
Other partially hydrogenated alkylaluminums etc.
In addition, compounds similar to these can be listed.
and two or more aluminum atoms via oxygen atoms or nitrogen atoms.
can be mentioned as organoaluminum compounds in which
Ru. Examples of such compounds include (C2H5)
2AQ OAQ (C2H5)2, (C4He)2A
QoAt (C4H9)2, (C,H,), AQ N
AQ (C,H,)2, C2H. Methylaluminoxane can also be mentioned.
As a halogen-free organic A9 compound, group Ⅰ metals
A rusted product of aluminum and aluminum can also be used.
Examples of compounds include LiA It (C2H5) 4
, LiA Q (C7HIS) 4
I can do it. Among these, especially trialkyl aluminum or
is an aluminum compound in which two or more of the above aluminum compounds are combined.
Preferably, aluminum aluminium is used. these
The halogen-free organic AQ compound is preferably 70 mol% or less.
Preferably 40 mol% or less, particularly preferably 10 mol% or less
When used in combination with halogen-containing organoaluminum compounds in the amounts below:
You can also The ethylene/pentene-1 copolymer [0] co is the catalyst
obtained by conducting a polymerization reaction in a hydrocarbon solvent using the components
It will be done. Hydrocarbon solvents include pentane, hexane, and
Fats such as putane, octane, decane, dodecane, and kerosene
group hydrocarbons and their halogen derivatives. Cyclohexane, methylcyclopentane, methylcyclo
Alicyclic hydrocarbons such as hexane and their halogen derivatives
Body: Aromatic hydrocarbons such as benzene, toluene, xylene, etc.
and halogen derivatives such as chlorobenzene.
I can do it. In addition, the olefin itself used for polymerization is used as a liquid medium.
It can also be used as When carrying out a polymerization reaction, the reaction volume II! Hit, Chita
0.0005 to about 1 mmol, more preferably
about 0.001 to about 0.5 mmol, also organic aluminum
aluminum/titanium (atomic ratio) of about 1 to
about 2000, preferably about 5 to about 100.
It is better to use The polymerization temperature of the olefin is about 20 to about
300°C, preferably about 65 to about 250°C. Also
The polymerization pressure is atmospheric pressure ~ 3000 kg/Cm2-G
Preferably about 2 to about 100 kg/cm2-G, especially
Preferably about 5 to about 50 kg/cm2-G
. In olefin polymerization, water is used to adjust the molecular weight.
It is better to let the elements coexist. Polymerization can be carried out batchwise or continuously. It can also be carried out in two or more stages with different conditions.
Wear. The ethylene/pentene-1 copolymer composition according to the present invention
In this case, ethylene/pentene-1 copolymer (A) is used.
For example, ethylene-pentene-1 copolymer as mentioned above
Combine [1], [111 or [田], or this
A mixture of these can be used. (B) a-olefin random copolymer composition of the present invention
The a-olefin random copolymer (B) constituting the
Two types of repeats derived from different a-olefins
It is a copolymer in which units are randomly arranged. Ethylene prepared using ethylene as a pace monomer
a-olefin copolymer rubber This a-olefin random copolymer (B) is
Unlike tyrene/pentene-1 copolymer (A), it has low
Crystals that are crystalline or immaculate and measured by X-ray diffraction method
The degree of oxidation is 30% or less, preferably 25% or less. follow
So, this a-olefin random copolymer (B) has the following:
Many of them do not have a clear melting point. Furthermore, like this
Due to its low crystallinity, this α-olefin random copolymer
Coalescence (B) is the above-mentioned ethylene/pentene-1 copolymer (
It is softer than copolymer A), and the pull of this copolymer (B) is
Tension modulus is usually 0.1kg/cm2 to 1000
kg/cm2, preferably 1kg/cm2~800k
It is within the range of g/cm2. In this regard, the above ethylene
Tensile modulus of Tenten-1 copolymer (A) is usually 1
00kg/cm2 to 15000kg/cm2, preferably
is about 300kg/cm2 to 13000kg/cm2
Yes, harder than this σ-olefin random copolymer
It is a resin. In addition, the material of this σ-olefin random copolymer (B)
The melt index (measured at 190°C) is typically 0.1
~30g710min, preferably 1.0-20g710min
, particularly preferably within the range of 2.0 to 15 g/10 minutes.
Ru. Furthermore, the value of Mw/Mn measured by GPC is
Usually 5.5 or less, preferably 4.5 or less, particularly preferably
is 3.5 or less. Furthermore, such a-olefin random copolymers (
The glass transition temperature (Tg) of B) is usually 150 to +50
℃, preferably within the range of -80 to -20℃, and this
α-olefin random copolymer (B) at 135°C,
The intrinsic viscosity [7] measured in Karin is 0.2 to 10 d
l/g, preferably t< is preferably 1 to 5 dl/g.
Yes. In addition, its density is usually 0.82 to 0.96 g/
cm3, preferably in the range of 0.84 to 0.92 g/cm3
It is within the surrounding area. Substitute for α-olefin random copolymer (B) such as
Taking the typical examples of (a) ethylene/a-olefin copolymer rubber and (b) propylene/a-olefin copolymer rubber as examples.
I will explain in more detail. The above ethylene/a-olefin copolymer comb (a)
The constituent a-olefin usually has 3 carbon atoms.
~20 a~olefins, such as propylene, butene
-1, pentene-1, hexene-1,4-methylpente
ene-1, octene-1, decene-1 and mixtures thereof
I can name things. Among these, propylene and
and/or butene-1 are preferred. In addition, propylene/a-olefin copolymer rubber (b)
The constituent a-olefin usually has 4 carbon atoms.
~20 α-olefins, such as butene-1, pente
hexene-1,4-methylpentene-1, octane-1, hexene-1,4-methylpentene-1,
Mention may be made of ten-1, decene-1 and mixtures thereof.
I can do it. Among these, butene-1 is particularly preferred. Note that the a-olefin copolymer constituting the composition of the present invention
The body is within a range that does not impair the properties of the a-olefin copolymer.
Within, component units derived from diene compounds, etc.
Component units other than those derived from α-olefins
May contain. For example, in the a-olefin copolymer used in the present invention,
The component units that are allowed to be included are: 1.4
-hexadiene, 1,6-octadiene, 2-methyl
-1,5-hexadiene, 6-methyl-1,5-hebuta
chain such as gen, 7-methyl-1,6-octadiene
Component units derived from non-conjugated dienes; cyclohexadiene, dicyclopentadiene, methyltetra
Trahydroindene, 5-vinylnorbornene, 5-ethyl
tylidene-2-norbornene, 5-methylene-2-nor
Bornene, 5-impropylidene-2-norbornene
and 6-chloromethyl-5-isopropenyl-2-nor
Components derived from cyclic non-conjugated dienes such as bornene
Unit; 2.3-diisopropylidene-5-norbornene, 2-
ethylidene-3-isopropylidene-5-norbornene
and 2-propenyl-2,2-norbornadiene, etc.
Component units derived from diene compounds; and component units derived from cyclic olefin components are listed.
I can do it. In the a-olefin random copolymer
The content of the above-mentioned diene component units is usually 10
It is less than mol %, preferably less than 5 mol %. Ethylene/a-olefin copolymer (a) as above
, the molar ratio of ethylene and a-olefin (E
Tyrene/α-olefin) is a type of a-olefin.
Although it varies depending on the situation, it is generally 1/99 to 99/1, preferably
or 50150 to 9515. The above molar ratio is a
- 50150 if the olefin is propylene
~90/10 is preferable, and the a-olefin is
80 in the case of α-olefin having 4 or more carbon atoms
It is preferable that it is /20-9515. In addition, propylene/a-olefin copolymer (b)
The molar ratio of propylene to σ-olefin (prop.
Pyrene/α-olefin) is a type of a-olefin.
Although it varies depending on the number, it is generally between 50150 and 9515.
It is preferable. The above molar ratio is such that σ-olefin is 1-
When it is butene, it is 50150 to 90/10.
It is preferable that the a-olefin has 5 or more carbon atoms.
If it is an a-olefin, it is 80/20 to 9515.
It is preferable that there be. In the present invention, the above a-olefin graph
Among the above copolymers, the ethylene content is 35 to 50 mol%.
, ethylene/propylene random with crystallinity of 10% or less
Copolymer or ethylene/a-olefin random copolymer
The polymer has excellent effects on improving mechanical properties such as impact strength.
It is preferable because The above a-olefin random copolymer is usually
The above-mentioned ethylene/σ-olefin copolymer (a) and polymer
Lopyrene/a-olefin copolymer (b) is used alone
or used in combination, a-olefin random
The above a-oleph may be added within a range that does not impair the properties of the copolymer.
Random copolymers combine with other polymers or copolymers.
May contain. In the present invention, such other polymers or copolymers
Examples of compounds include aromatic vinyl hydrocarbons and conjugated dienes.
Copolymers or hydrides thereof can be mentioned. Ingredients
Physically, such aromatic vinyl hydrocarbons and conjugated diene
Styrene copolymers or their hydrides include styrene and butylene copolymers.
Tagene copolymer rubber, styrene/butadiene/styrene
Copolymer rubber, styrene/isoprene block copolymer
Body comb, styrene/isoprene/styrene block copolymer
Combined rubber, hydrogenated styrene/butadiene/styrene block
Copolymer rubber and hydrogenated styrene/isoprene/styrene
Ren block copolymer rubber can be mentioned. Composition The ethylene/pentene-1 copolymer composition of the present invention is as described above.
A specific ethylene/pentene-1 copolymer (A),
Contains a specific a-olefin random copolymer (B)
are doing. When two polymers are mixed, the resulting composition is
Demonstrates average or lower performance
However, as in the present invention, ethylene pentene
Random copolymerization of specific a-olefins into N-1 copolymer
By blending a small amount of body (B), ethylene and pente
without sacrificing the excellent properties of the Copolymer-1 copolymer.
Improved properties such as impact resistance, transparency, and low-temperature heat sealability.
In addition to improving impact resistance and ease of opening,
It is possible to form a well-balanced molded product.
. Ethylene-pentene-1 copolymer in the composition of the present invention
The blending ratio of (A) and a-olefin copolymer (B) is:
The weight ratio is within the range of 99:1 to 60:40. this
Ethylene-pentene-1 copolymer (A) in such a ratio as
By blending with the a-olefin copolymer (B)
, the balance between unsealability and impact resistance of molded objects, especially films.
It is possible to take the following steps. Furthermore, the combined weight of both
It is preferable to keep the quantitative ratio within the range of 95:5 to 70:30.
Ideally, it should be within the range of 90:10 to 80:20.
This provides a particularly good balance between ease of opening and impact resistance.
. The ethylene/pentene-1 copolymer composition according to the present invention
are heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, and slip agents.
, anti-blocking agents, anti-fog agents, lubricants, dyes, pigments,
Can contain natural oils, synthetic oils, waxes, etc.
The blending ratio is an appropriate amount. For example, as an optional component
Specifically, Tetrakis [Metal] is used as a stabilizer.
Tyrene-3 (3゜5-di-t-butyl-4-hydroxy
phenyl)propionate comethane, β-(3,5-di
-t-butyl-4-hydroxyphenyl)propionic acid
Alkyl ester, 22°oxamide bis[ethyl-3
(3,5-di-t-butyl-4-hydroxyphenyl)
Phenolic antioxidants such as copropionate,
Zinc arinate, calcium stearate, 12-hydro
Fatty acid metal salts such as calcium xystearate,
Serine monostearate, glycerine monolaurate,
Glycerin distearate, pentaerythritol mono
stearate, pentaerythritol distearate,
Polyhydric alcohols such as pentaerythritol tristearate
Examples include fatty acid esters of alcohols. this
They may be blended alone, but they may also be blended in combination.
Often, for example, tetrakis[methylene-3(3,5-
di-t-butyl-4-hydroxyphenyl)propione
Tocomethane and zinc stearate and glycerin mono
Examples include a combination with stearate. In particular, the present invention uses phenolic antioxidants and polyhydric antioxidants.
Use in combination with fatty acid ester of alcohol
is preferable, and the fatty acid ester of the polyhydric alcohol is trivalent.
Some of the alcoholic hydroxyl groups of the above polyhydric alcohols are
It is a esterified polyhydric alcohol fatty acid ester.
is preferable. Such fatty acid esters of polyhydric alcohols include:
Specifically, glycerin monostearate, glycerin
monolaurate, glycerin monomyristate, glycerin
Phosphorus monopalmitate, glycerin distearate, glycerin
Glycerin fatty acid esters such as lycerin dilaurate,
Pentaerythritol monostearate, pentaeryth
litol monolaurate, pentaerythritol dilaurate
rate, pentaerythritol distearate, penta
Pentaerythritol such as erythritol tristearate
fatty acid esters of alcohol are used. Such phenolic antioxidants can be used in the compositions of the present invention.
Usually 10 parts by weight of the resin component in the
Parts by weight or less, preferably 5 parts by weight or less, more preferably
is used in an amount of 2 parts by weight or less, and polyhydric alcohol
Fatty acid ester is 10 parts by weight per 100 parts by weight of the resin component.
It is used in an amount of not more than 5 parts by weight, preferably not more than 5 parts by weight. In the present invention, to the extent that the purpose of the present invention is not impaired,
Silica and silicon are added to the ethylene/pentene-1 copolymer composition.
Algae, alumina, titanium oxide, magnesium oxide, pumice
grains, pumice balloon, aluminum hydroxide, magne hydroxide
Si, basic magnesium carbonate, dolomite, sulfuric acid
Calcium, potassium titanate, barium sulfate, sulfite
Calcium, talc, clay mica, asbestos, gas
Rusty fiber, glass flakes, glass beads, calcium silicate
Cium, montmorillonite, bentonite, graphite
aluminum powder, molybdenum sulfide, boron fiber, charcoal
Silicone fiber, polyethylene fiber, polypropylene fiber
Contains fillers such as , polyester fiber, polyamide fiber, etc.
You may. The ethylene/pentene-1 copolymer composition according to the present invention
As for the manufacturing method, known methods can be applied, and
Ethylene/pentene-1 copolymer (A), specific σ-
Olefin random copolymer (B) and optionally added
Other ingredients to be added are mechanically blended using an extruder, kneader, etc.
or use a suitable good solvent, e.g.
hexane, heptane, decane, cyclohexane, ben
Simultaneously dissolved in hydrocarbon solvents such as zene, toluene, and xylene.
Dissolve or dissolve each separately and then mix to remove the solvent.
How to remove or even combine these two methods
For example, there are methods for doing this. Film The film of the present invention is made of ethylene pentene as described above.
-1 copolymer composition. The film of the present invention can be produced by either the melt method or the solution method.
It can also be manufactured by the method. For example, if a melting method is used
Calendar method, inflation method, T-die method
Any method can be adopted. Also,
When using the melting method, the endless belt method or
can also adopt a dry method such as the drum method,
It is also possible to adopt a wet method. In particular, the file of the present invention
can be advantageously manufactured by adopting the melting method.
I can do it. The film of the present invention can be unstretched, -axially stretched, or biaxially stretched.
It may be in a misaligned state. There is no particular limit to the thickness of the film of the present invention, but usually,
It is within the range of 10 μm to 3 μm. Therefore, in the present invention
``Film'' is a film used in the sense of boat fishing.
This term includes not only films but also so-called sheets. Such a film of the present invention can also be used alone.
It can be laminated with other resin films or metal thin films.
Composite films can also be used. Furthermore, the present invention
Pigments or dyes are applied to the surface of the film or the above composite film.
materials, metal powders, photosensitive materials, magnetic materials, magneto-optical materials, etc.
The method of the present invention is applied by applying a film-forming material dispersed in a binder.
Other properties can also be imparted to the film. Effects of the Invention The composition of the present invention has linear properties in terms of transparency, ease of opening, and impact resistance.
Recognized as low density polyethylene (LLDPE)
ethylene and an α-olefin having 4 or 6 carbon atoms.
superior to copolymers. Therefore, the resin composition of the present invention is particularly suitable for packaging films.
Suitable for film applications such as containers, etc., and other applications such as infusion containers, etc.
Hollow molded products, rotary molded products, injection molded products, and other films
Its properties can also be utilized in applications such as composite films laminated with
can be used. [Example] The present invention will be explained below with reference to Examples.
However, the invention is not limited to the examples. Example 1 <Production of ethylene/pentene-1 copolymer>
Preparation of medium components] 476 g of commercially available anhydrous magnesium chloride was added under a nitrogen atmosphere.
Suspended in n-decane 109, oleyl alcohol 4.
Add 0 kg and react at 135°C for 5 hours without stirring.
I set it. As a result, a colorless and transparent liquid was obtained. After lowering the temperature of this solution to 110°C, 0.45 mol of T I (OC2H5) 4 was added,
The reaction continued at 110°C for 5 hours. The resulting solution was heated at room temperature.
saved. [Polymerization] Dehydrated and purified using a continuous polymerization reactor with an internal volume of 200Q.
Hexane at 100Q/hour, ethylaluminum sesqui
19.9 mmol/h of chloride,
Tan catalyst component converted to Ti atom is 0.50 mmol/
It was fed continuously at the rate of time. At the same time, ethylene
13Kg/hour, 2.2Kg/hour of Pentene-1,
Hydrogen was continuously supplied at a rate of 9.097 hours to maintain the polymerization temperature.
degree 170℃, total pressure 31Kg/Cm2-G. Residence time 1 hour, copolymer concentration relative to solvent hexane
Copolymerization was carried out under conditions of 105 g/Q. The obtained copolymer has a melt flow rate (190°C)
is 2.2g/10min, density is 0.935g/Cm3,
The structural unit derived from pentene-1 is 4.1% by weight, R
S is 34 (impact strength -1700+tg -Cm/Cm
, tear strength in the pulling direction = 50Kg/cm), H
h/HQ is 3.4. <Production of composition> After blending the above copolymer with a heat-resistant stabilizer, it is melt-extruded to form pellets.
It has been made into a For 90 parts by weight of the pellets, ethylene
・Butene-1 copolymer rubber (melt index 4.0
, butene-1 content 12 mol% Mw/Mn=2.5.
Tensile modulus 300-17cm, crystallinity 2
3% and 10 parts by weight of pellets and mixed in a V-type blender.
It matched. <Film forming> Using a commercially available tubular film forming machine for polyolefin.
Form a film with a width of 180mm and a thickness of 0.03mm.
Ta. The resin temperature during molding was 180°C, and the extruder nozzle was
Crew rotation speed 6Or, p, m, die diameter 100mm
φ die slit width 0.5mm, cooling air ring - stage
went. Evaluation of the film> The tensile properties of the formed film are as per ASTM-D882.
Law 1. Impact strength is determined by the method of AS TM-D342o.
, pull! Strength tiA S TM-D-1004 method
, transparency is AS TM-Dl 003 (7)? H
, :, Heat sealability was measured according to JIS x1707.
Established. The results are shown in Table 1.

[In Example 1, the blending weight ratio of ethylene/pentene-1 copolymer and ethylene/butene-1 copolymer rubber was 8.
A composition was prepared in the same manner as in Example except that the ratio was 0:20, and a film was made using this composition. The properties of this film are shown in Table 1. Example 3 In Example 1, the blending weight ratio of ethylene/pentene-1 copolymer and ethylene/butene-1 copolymer rubber was changed to 7.
A composition was prepared in the same manner as in Example 1 except that the ratio was 0:30, and a film was made using this composition. The properties of this film are shown in Table 1. Example 4 In Example 1, the melt flow rate (190°C) obtained by changing the supply ratio of ethylene, n-pentene-1, and hydrogen was 1.6 g/10 minutes, and the density was 0.
．． 927 g/cm', monomer equivalent content of repeating units derived from pentene-1 is 9.2% by weight, R
S is 41.7 (impact strength == 2000Kg-cm/
cm, tear strength in the pulling direction -48Kg/cm),
A composition was prepared in the same manner as in Example 2 except that an ethylene/pentene-1 copolymer having Hh/HQ of 2.3 was used, and a film was made using this composition. The properties of this film are shown in Table 1. Example formula The copolymer obtained by changing the supply ratio of ethylene, n-pentene-1 and hydrogen in Example 1 is as follows:
The melt index (190°C) was 2.2 g/10 min, the density was 0.921 g/Cm3, and the structural unit derived from pentene-1 was 12% by weight. In addition, the ratio (RS) of the impact strength to the tear strength in the take-off direction of the copolymer was 50 (impact strength = 3000 kg
-cm/cm, tear strength in the pulling direction = 60Kg
/cm). The same procedure as in Example 2 was conducted except that an ethylene/pentene-1 copolymer whose H h,/HR obtained from the DSC melting peak pattern of the copolymer was 1.5 was used. The results are shown in Table 1. Comparative Example 1 In Example 1, a film was created using only the ethylene/pentene-1 copolymer without using the ethylene/butene-1 copolymer rubber. The properties of this film are shown in Table 1. Comparative Example In Example 4, the ethylene-pentene-1 copolymer rubber prepared in Example 4 without using the ethylene-butene-1 copolymer rubber was
A film was made using only one copolymer. The properties of this film are shown in Table 1. Comparative Example 3 In Example 5, the ethylene-pentene-1 copolymer rubber prepared in Example 5 was used without using the ethylene-butene-1 copolymer rubber.
A film was made using only one copolymer. The properties of this film are shown in Table 1. Comparative Example 4 In Example 1, the blending weight ratio of ethylene/pentene-1 copolymer and ethylene/butene-1 copolymer rubber was 5.
A composition was prepared in the same manner as in Example 1 except that the ratio was changed to 5:45, and a film was made using this composition. The properties of this film are shown in Table 1. Comparative Example 5 The same procedure as in Example 2 was carried out except that Moretic 0234M (Note) manufactured by Idemitsu Petrochemical Industries Ltd. was used in place of the ethylene-pentene-1 copolymer of Example 1. The results are shown in Table 1. Note) Moretic 0234M (ethylene-butene-1 copolymer) Melt flow rate (190°C) 2.25g710
Part density 0.923g/cmA RS 19.0 (Impact strength - 800Kg-cm/Cm, tear strength =
42Kg/cm) Hh/Hi+ 1.8 Comparative Example 6 The same procedure as Example 2 was carried out except that LLDPE FG326 (Note) manufactured by Nippon Unicar was used instead of the ethylene/pentene-1 copolymer of Example 1. . The results are shown in Table 1. Note) FG326 (ethylene/hexene-1 copolymer) melt flow rate (190℃) 0.86g/1
0 minute density 0.923g/cm3 RS21 (Impact strength = 2900Kg-cm/cm. Tear strength = 140Kg/cm) There is only one melting peak at 124°C. Comparative Example 7 In place of the ethylene-pentene-1 copolymer of Example 1, Tsurtozex 2020L (note) manufactured by Mitsui Petrochemical Industries, Ltd.
The same procedure as in Example 2 was carried out except that . The results are shown in Table 1. Note) Urtozex 2020L (ethylene/4-methyl-pentene-1 copolymer) Melt flow rate (190°C) 2.1g/1
0 minute density 0.920g/c
mARS 32.4 (Impact strength = 3400Kg-cm/am. Tear strength = 105Kg/cm) Hh/Hc 1.4

[Brief explanation of the drawing]

Figure 1 shows the DSC melting peak pattern obtained by measuring the "super slowly cooled sample" of the ethylene/pentene-1 copolymer used in the present invention under normal measurement conditions, and Figure 2 shows the DS obtained by measuring a normally slowly cooled sample of the ethylene/pentene-1 copolymer used under normal measurement conditions
C melting peak pattern.

Claims (2)

[Claims] (1) (A) An ethylene/pentene-1 copolymer having a repeating unit derived from ethylene and a repeating unit derived from pentene-1, and (a) Melt flow rate measured by ASTM D1238E. is 0.01 to 100g/10 minutes, (
b) Density measured by ASTM D1505 is 0.
87 to 0.96 g/cm^3, and (c) the content of repeating units derived from pentene-1 in the ethylene/pentene-1 copolymer is 1 to 25 in terms of monomers.
% by weight, and (d) the ratio (RS) of the impact strength of a 40 μm thick film obtained by molding the ethylene/pentene-1 copolymer to the tear strength in the pulling direction of the film is: RS≧-20logMFR-1000d+968 (where MFR represents the melt flow rate of the copolymer, d
represents the density of the copolymer); and (B) a low-crystalline to non-crystalline α-polymer having at least two types of repeating units derived from different α-olefins. Olefin random copolymer and 9
An ethylene/pentene-1 copolymer composition containing the ethylene/pentene-1 copolymer at a weight ratio of 9:1 to 60:40. (2) (A) An ethylene/pentene-1 copolymer having a repeating unit derived from ethylene and a repeating unit derived from pentene-1, and (a) Melt flow rate measured by ASTM D1238E. is 0.01 to 100g/10 minutes, (
b) Density measured by ASTM D1505 is 0.
87 to 0.96 g/cm^3, and (c) the content of repeating units derived from pentene-1 in the ethylene/pentene-1 copolymer is 1 to 25 in terms of monomers.
% by weight, and (d) the ratio (RS) of the impact strength of a 40 μm thick film obtained by molding the ethylene/pentene-1 copolymer to the tear strength in the pulling direction of the film is: RS≧-20logMFR-1000d+968 (where MFR represents the melt flow rate of the copolymer, d
represents the density of the copolymer); and (B) a low-crystalline to non-crystalline α-polymer having at least two types of repeating units derived from different α-olefins. Olefin random copolymer and 9
A film comprising an ethylene/pentene-1 copolymer composition containing a weight ratio of 9:1 to 60:40.