JPS62121709A - Lowly crystalline ethylene random copolymer and its production and use - Google Patents

Abstract

PURPOSE:To obtain the title copolymer which is narrow in both MW distribution and composition distribution and can give a composition excellent in transparency, surface nonstickiness, impact resistance, heat sealability, etc., by copolymerizing ethylene with a 3-20C alpha-olefin. CONSTITUTION:Ethylene (A) is copolymerized with a 3-20C alpha-olefin (B) at -50-200 deg.C in the presence of a catalyst comprising a zirconium hydride compound in which the ligand is a group containing conjugated pi electrons [e.g., bis(cyclopentadienyl)zirconium monochloride hydride] and an aluminooxane of formula I or II (wherein R is a hydrocarbon group and M>=20). In this way, the title copolymer containing 35-85wt% component A and 65-15wt% component B, having an intrinsic viscosity of 0.5-10dl/g (in decalin at 135 deg.C), a MW distribution <=2.5 (GPC), a crystallinity <=30% and a boiling methyl acetate- soluble portion <=2wt% and satisfying the relationship: 1.05<=B<=2 (wherein B is a value of formula III, wherein PE is the molar fraction of component A in the copolymer, PO is the molar fraction of component B and POE is the molar fraction of A-B chains in the total dyad chains) is obtained.

Description

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

[Conventional technology]

Conventionally, demand for low-crystalline ethylene/α-olefin copolymers has been increasing for applications such as soft molding applications and modifiers for various resins. The manufacturing method is
A method is known in which ethylene and α-olefin are copolymerized in the presence of a titanium-based catalyst made of a titanium compound and an organoaluminum compound, or a vanadium-based catalyst made of a vanadium compound and an organoaluminum compound. Low-crystalline ethylene/α-olefin copolymers obtained with tethane-based catalysts generally have a wide molecular weight distribution and composition distribution;
Moreover, the transparency, surface non-adhesiveness, and mechanical properties were poor. In addition, low-crystalline ethylene/α-olefin copolymers obtained with vanadium-based catalysts have narrower molecular weight distribution and composition distribution than those obtained with titanium-based catalysts, and have transparency, surface non-adhesion, and mechanical properties. Although there is a slight improvement in these properties, it is still insufficient for applications requiring these properties, and there is a need for low-crystalline ethylene/α-olefin copolymers with further improved properties.

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

JP-A No. 58-19309 describes the following formula % formula % where R is cyclopentadienyl, 01-C0-alkyl, /.logen, Me is a transition metal, Ha
l is a halogen, and a transition metal-containing compound represented by the following formula %)) where R is methyl or ethyl and a number from 4 to 20, a linear aluminoxane or The following formula % formula %) Here, the definitions of R and n are the same as above, In the presence of a catalyst consisting of a cyclic aluminoxane represented by A method of polymerizing the above at a temperature of -50°C to 200°C is described. The same publication states that in order to adjust the density of the resulting polyethylene, ethylene should be polymerized in the presence of a small amount of α-olefin or a mixture of up to 10% of a rather good chain. There is.

Japanese Patent Application Laid-open No. 59-95292 describes the following formula, where n
is 2 to 40, and R is 01 to C6 alkyl, and a linear aluminoxane represented by the following formula where n
The same publication describes an invention relating to a method for producing a cyclic aluminoxane represented by the following, in which the definitions of and R are the same as above, and which was produced by the same method. For example, when olefin polymerization is carried out by mixing methylaluminoxane and a bis(cyclopentagenyl) compound of titanium or zirconium, the amount of olefin polymerization per 14 transition metals and per hour is
It is stated that more than 25 million 2 polyethylene can be obtained.

JP-A-60-35005 describes the following formula where R
1 is 01-C10 alkyl, Ro is R1 or combined to represent 10-, an aluminoxane compound represented by is first reacted with a magnesium compound, then the reaction product is chlorinated, and further Ti, V , a method for producing a polymerization catalyst for olefins by treatment with a compound of Zr or Cr is disclosed. The publication states that the above catalyst is particularly suitable for copolymerizing a mixture of ethylene and a C8 to C12 α-olefin.

JP-A No. 60-35006 discloses that mono-, di- or tri-cyclopentadienyl of two or more different transition metals or its rust conductor (a) and alumoxane (aluminoxane) are used as a catalyst system for producing a reactor blend polymer. )
Combination (b) is disclosed. In Example 1 of the same publication, ethylene and propylene were polymerized using bis(pentamethylcyclopentadienyl)zirconium dimethyl and alumoxane as catalysts, and the number average molecule i was 15.3.
00, a weight average molecular weight of 36.400 and a propylene content of 3.4%. In addition, in Example 2, bis(pentamethylcyclopentadienyl)zirconium dichloride,
Ethylene and propylene are polymerized using bis(methylcyclopentadienyl)zirconium dichloride and alumoxane as catalysts to form a number-average molecule of 1Z200X'￥M M
c average molecular weight 11,900 and a toluene soluble portion containing a 300 molar width propylene component and a number average molecular weight 13,000;
A number average molecular weight of 2 consisting of a toluene insoluble portion containing propylene components with weight average molecular weights of 7, 400 and 4.8 molar widths.
,000, heavy! A blend of polyethylene and ethylene-propylene copolymer is obtained containing an average molecular weight of -38,300 and a propylene component of over 7.1 moles. Similarly, in Example 3, the molecular weight distribution (Mw/M n ) was 4.57.
A blend of LLDPE and ethylene-propylene copolymer is described, which consists of a soluble portion with a 20.6 molar width of the propylene component and an insoluble portion with a molecular ↑ distribution of 3.04 and a 2.9 molar width of the propylene component. .

JP-A No. 60-35007 describes ethylene alone or together with an α-olefin having 3 or more carbon atoms and a metallocene with the following formula (%), where R is an alkyl group having 1 to 5 carbon atoms, and n is 1
Polymerized in the presence of a catalyst system comprising a cyclic alumoxane or a linear alumoxane represented by the following formula %, which is an integer of ~20, or a linear alumoxane represented by the following formula %, where R and n are defined as above. It describes how to do this. According to the description in the same publication, the polymer obtained by this method has a molecular weight of about 500 to about 1
It has a weight average molecular weight of 400,000 and a molecular weight distribution of 1.5 to 4.0.

Also, in Japanese Patent Application Laid-Open No. 60-35008, there is a
It is described that polyethylene or copolymers of ethylene and α-olefins of C1 to CIo having a wide molecular weight distribution can be produced by using a polymeric system containing a metallocene and an alumoxane. The publication describes that the above copolymer has a molecular weight distribution (Mw/Mn) of 2 to 50.

Furthermore, JP-A No. 60-35009 discloses that by using a catalyst system containing a vanadium compound and an organoaluminum compound, molecular weight distribution (ΩW/Mn') y5Z
A method for making copolymers of ethylene and α-olefins with a low A of less than 2 is disclosed.

[Problem that the invention seeks to solve]

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

Another object of the present invention is that the molecular weight distribution and composition distribution are narrow;
The object of the present invention is to provide an ethylene-based random copolymer that has excellent transparency, surface non-adhesiveness, and mechanical properties and has low crystallinity.

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

Still another object of the present invention is to provide a low-crystalline random copolymer that provides a composition with excellent heat-sealability when blended with a thermoplastic resin.

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

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

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

[In the formula, PE represents the molar fraction of the ethylene component in the copolymer, PO represents the molar fraction of the α-olefin component, and POg represents the molar fraction of α-olefin/ethylene chains in all dyad chains. show the rate]

The B value expressed by is in a range that satisfies the following formula (II): 1.05≦B≦2 (II), and the R junction in the copolymer main chain is present in the (f)+30-NMR spectrum. and (g) a boiling methyl acetate soluble portion is less than or equal to a zo heavy plate. This is achieved by system random co-vehicle merging.

According to the present invention, the low multiplicity ethylene-based random co-domerized compound of the present invention comprises (A) a zirconium hydride compound having a group having a conjugated electron as a ligand, and (B'l aluminoxane). In the presence of a binder consisting of ethylene and 3 to 2 carbon atoms,
It can be produced by the method of the present invention in which 0 α-olefins are copolymerized.

The above-mentioned zirconium hydride compound (A) having a group having a conjugated 7C, [child as a ligand can be used, for example, by the following formula (II
) R,'R'R,'ZrH (II) Here, R1 represents a cycloalkagenyl group, and R1 and R3 are a cycloalkagenyl group, an aryl group, an alkyl group, a hydrogen atom, or a hydrogen atom. , is a compound represented by.

Examples of the cycloalkagenyl group include a tfd dicyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopendagenyl group, a dimethylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, and the like. Examples of the alkyl group for R2 and R3 include a methyl group, ethyl group, propyl group, indenyl group, butyl group, and examples of the aryl group include a phenyl group, benzyl group, and neophyl group. Examples of the halogen atom include fluorine, chlorine, and bromine. Examples of the zirconium hydride compound include the following compounds.

Bis(cyclopentagenyl)zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium monopromide monohydride, Bis(cyclopentagenyl)methylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride, Bis (cyclopentagenyl)cyclohexylzirconium hydride, bis(cyclopentagenyl)phenylzirconium hydride, bis(cyclopentagenyl)benzylzirconium hydride, bis(cyclopentagenyl)neopentylzirconium hydride, bis(methylcyclopentagenyl) ) Zirconium monochloride monohydride, bisindenylzirconium monochloride monohydride, The above zirconium hydride compounds can be used as they are, but they can also be used with toluene, etc. such as bis(cyclopentagenyl)zirconium monochloride monohydride. It is preferable to use a compound that is poorly soluble in a solvent after contacting it with an organoaluminum compound. By this operation, a zirconium hydride compound that is poorly soluble in a solvent can be made easily soluble in a solvent.

Specifically, the organoaluminum compounds to be brought into contact with the zirconium hydride compound include trialkyl aluminum such as trimethylaluminum, triethylaluminum, and tributylaluminum, dribble kenylaluminum such as triisoprenylaluminum, dimethylaluminum methoxide, and diethylaluminum ethoxy R1°AI (OR2) in addition to dialkylaluminum alkoxides such as dibutylaluminum butoxide, alkylaluminum sesquialkoxides such as methylaluminum sesquimethoxide, and ethylaluminum sesquiethoxide. 1. Partially alkoxylated alkyl aluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, alkyl alkyls such as methylaluminum sesquichloride, ethylaluminum sesquichloride, etc. with an average composition of Examples include partially halogenated aluminum alkyls such as aluminum sesquihalide, methylaluminum dichloride, and alkylaluminum cybarides such as ethylaluminum dichloride.

The reaction of both compounds is preferably carried out in a hydrocarbon medium while blocking light, and the mixed molar ratio (Al/Zr) of the organoaluminum compound and zirconium compound is 0.5 to 30, preferably 1 to 20, The concentration of zirconium in the liquid phase 1 is 1 to 1 mole of O,OO, preferably 5 to 0 of O,OO.
．． It is sufficient to keep the amount of the two moles in contact with each other at a reaction temperature of about 0 to 120°C. As the above hydrocarbon medium,
It can be selected from those exemplified as the polymerization solvent described later.

Specifically, the aluminoxane (B) of the catalyst component used in the method of the present invention is represented by the general formula (IV) or the general formula (v) (wherein, lt represents a hydrocarbon group, and m is preferably 20
or more, and particularly preferably an integer of 25 or more). In the aluminoxane, R is a hydrocarbon group such as methyl group, ethyl group, propyl group, butyl group, preferably methyl group or ethyl group, particularly preferably methyl group, m is preferably 1 is It represents an integer of 20 or more, particularly preferably an integer of 25 or more, particularly preferably an integer of 30 to 100. As a method for producing the aluminoxane, the following method can be exemplified.

(]) Trialkyl aluminum 6m is added to a suspension in a hydrocarbon medium of compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride hydrate, copper oxalate hydrate, aluminum sulfate hydrate, etc. A method of adding and reacting.

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

Among these methods, method (I) is preferably employed. Note that the aluminoxane may contain a small amount of organometallic component.

In the method of the present invention, the raw material supplied to the polymerization reaction system is a mixture of ethylene and an α-olefin having 3 to 20 carbon atoms other than ethylene. The content of ethylene in the polymerization raw material olefin is usually 10 to 90 mol %, preferably 20 to 80 mol %, and the content of the α-olefin is usually 10 to 90 mol %, preferably 20 mol %. The content ranges from 80% to 80% by mole.

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

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

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

The proportion of the zirconium hydride compound (A) used when carrying out the method of the present invention by liquid phase polymerization is usually 10-8 as the concentration of zirconium metal atoms in the polymerization reaction system.
from 10-2 gram atom/1° preferably 10-7
and 10-3 gram atoms/l. -Also, the proportion of aluminoxane used is usually 10-4 to 10 degrees, assuming 6 degrees of aluminum atoms in the polymerization reaction system.
1 gram atom/1° preferably 10-3 to 5 X
The ratio of aluminum gold atoms to zirconium metal atoms in the polymerization reaction system is usually in the range of 25 to 10', preferably 1.
The range is from 02 to 106. The molecular weight of the copolymer is
It can be adjusted by hydrogen and/or polymerization temperature.

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

The composition of the low crystalline ethylene copolymer of the present invention is such that the ethylene component is 35 to 85% by weight, preferably 40 to 8% by weight.
The amount of ON is in the range of 15 to 65, preferably 20 to 60, by weight of the α-olefin component.

Furthermore, the low crystalline ethylene random copolymer of the present invention is
The value of the intrinsic viscosity [η] measured in decalin at 135°C is 0.5 di/? , preferably 1 to 6 dt/? has a value in the range of .

In addition, the molecular weight distribution (M w / M n ) of the low-crystalline ethylene copolymer measured by gel A = migration chromatography (GPC) is 25 or less, and the molecular weight is 2.3 or less, particularly favorable. It is in the range of 2 or less.

When the molecular weight distribution of the low-crystalline ethylene copolymer is greater than 25, the copolymer may become more sticky (8) the composition containing the copolymer as a modifier may become more sticky,
Since it will cause blocking, it must be within the above range.

Indeed, the low crystallinity ethylene copolymer has low crystallinity, and its crystallinity determined by X-ray diffraction is 30% or less, preferably 20% or less, and particularly preferably in the range of O to 15%. be.

The Mw/Mn value is measured as follows according to "Kölpermeation Chromatography" written by Takeuchi and published by Maruzen.

(I) Using standard polystyrene with a known molecular weight (monodispersed polystyrene manufactured by Toyo Soda Co., Ltd.), the molecular weight M and the
PC(()el Permeation Chro-
matograph) counts and molecular weights M and E
Create a correlation chart calibration curve for V (Blution Volume). The concentration at this time is 0.02 wt'l.

(2) Obtain a GPC chromatograph of the υ sample by GPC measurement, calculate the fi average molecular weight Mn and weight average molecular weight Mw in terms of polystyrene from the above (I) K, and calculate qw/1'vl.
Find the n value. Sample preparation conditions and GPC
The measurement conditions were the following 11 conditions.

[Sample preparation]

(a) Separate the sample into an Erlenmeyer flask together with the O-dichlorobenzene melt to a concentration of 0.1 wt%.

(b) Add anti-aging agent to the Erlenmeyer flask containing the sample.
Add 0.05 wt % of 6-sheet tert-B-P-/yvdur to the polymer solution.

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

) Apply the stock solution to opcH.

[() P C measurement conditions] It was conducted under the following conditions.

(a) Equipment ft Water 5 company 131 (I5Q
C-AI, C/GPC) (b) Column Toyo Soda (GM) (type) 1400 μt sample)) Temperature 140°C (e) Flow rate 1 a//min Sada et al. The low crystalline ethylene copolymer has the following formula (I) [where h indicates the mole fraction of the ethylene component in the copolymer, and PO indicates the mole fraction of the α-olefin component. Show POI! ! represents the mole fraction of α-olefin/ethylene chains in all dyad chains] The value of 13 expressed by the following formula (II) 1.05≦B≦
2 (I1).

The above B value is an index representing the distribution state of each heptamer component in the copolymer chain; o, 1. 'Ray (Mac
romolecules, 10, 773 (I9
77)), J. C. Randall (Macrom
olecules, 15°353 (I9B2), J.
Polymer 5science.

Polymer Physics gd,, 11,
275 (I973)).

K, Kimura (POlymer, 25,441 (I
Based on the report of 984)) et al., PE and PO defined above
and P□+e. The larger the Joki B value, the fewer block-like chains, the more uniform the distribution of ethylene and α-olefin, and the more narrow the composition distribution of the copolymer.

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

When the ethylene content of the copolymer is 50 moles or less: 1.0 + 0.3 5 x P v≦B≦1/(I-PE
), when the ethylene content of the copolymer is 50 moles or more: 1, 3-0.3 X P≦B≦1/gie.

More preferably general formula %formula% Especially preferred is the general formula 1.5-0.5XP1! i≦B≦l　/g　E　.

The composition distribution B value is approximately 200% in a 10mm diameter sample tube.
Tn1? The IsC-NMR spectrum of a sample obtained by homogeneously dissolving Ji [coalescence of
MITz, Spectrum @ 1500 Flz%
Measurement was performed under the following measurement conditions: filter fnr 1500 Hz, pulse edge υ return time 4.2 sec, pulse width 7 μsec, and number of integrations 2000 to 5000 times, and PE and POLrom were calculated from this spectrum. Furthermore, in the 13C-NMR spectrum of the low-crystalline ethylene copolymer of the present invention, there are αβ and βγ signals based on methylene chains between two adjacent tertiary carbon atoms in the copolymer main chain. Not observed. For example, in a copolymer of ethylene and 1-hexene, the following bonds: C4H, C4T-T.

When viewed from the tertiary carbon on the left derived from 1-hexene, the three methylene groups in the center are located at positions α, β, and r from the left, while when viewed from the tertiary carbon on the cloth side, they are located at positions α, β, and r from the right. β,
It is located at r. Therefore, although there is a methylene group giving αγ and ββ signals in the above bonding unit, αβ
and there is no methylene group giving a βγ signal.

Similarly, the following bond in which 1-hexene is bonded head-to-tail:
In α -CHCH, -CHCH, - 1α I C414+l C4H9, there is only a methylene group that gives an αα signal, and there is no methylene group that gives an αβ or βγ signal.

On the other hand, the following bonds α β γ a -CHCH, -CHtCH, -CH, CH- and 1
δ r β α l C, H, C, H.

α β -CHCH, C) TtCH- 1β α I C4H11C4H0 each has a methylene group giving a βγ signal and an αβ signal.

As is clear from the above explanation, it can be seen that in the low crystalline ethylene copolymer of the present invention, the bonding direction of the monomer copolymerizable with ethylene is regular.

The boiling methyl acetate soluble content of the low crystalline ethylene random copolymer of the present invention is 2 weight or less, preferably 1.5 to
The range is 0.01% by weight, particularly preferably 1.0 to 0.03% by weight, particularly preferably 0.7% to 0.03% by weight. When the weight fraction of the ethylene component compensation of the low crystalline ethylene random copolymer is PEW, the boiling methyl acetate soluble content of the core low crystalline ethylene random copolymer [Ex weight ratio, preferably More preferably, EX≦2.2-2XPEW, Exi 1.35"W, and particularly preferably, IX≦0.9-0.6XPEW.

Measurement of boiling methyl acetate extraction 31 was performed by preparing a press sheet with a thickness of 1 u from the sample, and then pressing this press sheet into a 2
The pieces cut into X 2 y angles were placed in a cylindrical glass filter and subjected to reflux for 6 hours using a Soxhlet extractor at a reflux frequency of about 75 minutes each time. The amount of extraction was determined by drying the extracted residue in a vacuum dryer until it reached constant f.

The low crystalline ethylene random copolymer of the present invention usually has 0
．． It has a density of 90t/cc or less. Also, the stress at break and the groan at break are each 300 kl; // C'm
"Hereafter, it is 400 clr or more.The density was measured after heat treating the sample at 120 ° C. for 1 hour and slowly cooling it to room temperature over 1 hour.The stress at break and the depth at break were measured using a ring-shaped test piece ( A specimen having an inner diameter of 18 u+, an outer diameter of 22 u, and a thickness of 1 u) was prepared and measured at a tensile rate of 500 mm/min and a measurement temperature of 25°C.

The low-crystalline ethylene-based random copolymer of the present invention has a narrower molecular fold distribution and compositional distribution than copolymers obtained using titanium-based catalysts, and has transparency, surface non-adhesiveness, and mechanical properties. It can be said that it is excellent in Furthermore, when compared with a copolymer obtained using a vanadium catalyst, the molecular weight distribution and composition distribution are approximately the same or narrower, but it can be said that the arrangement state within the molecular chain of the copolymerized components is different.

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

By blending the low-crystalline ethylene-based random copolymer of the present invention with other ethylene-based polymers containing ethylene as a main component, such as polyethylene, the impact resistance, especially low-temperature impact resistance, of the other ethylene-based polymers can be improved. , an ethylene polymer composition with improved bending resistance and low-temperature heat-sillability is obtained, and furthermore, the ethylene polymer composition has transparency and surface non-adhesion due to the combination of a low-crystalline ethylene random copolymer. It has the characteristic that it does not cause a decrease in Other ethylene polymers mentioned above (high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene topropylene, 1-7" ten, l-hexene, 4-methyl-1
- 3 to 20 carbon atoms, such as pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc.
Examples include ethylene-based copolymers containing ethylene as a main component, which are copolymers with α-olefins. Its intrinsic viscosity [η], measured in decalin at 135° C., is usually in the range 0.5 to 20 dl/f.

When the low-crystalline engineered ethylene random copolymer of the present invention is blended with the other ethylene polymer, the blending ratio is 1001 parts of the other ethylene polymer to 0.5 parts of the other ethylene polymer.
The amount ranges from 1 to 30 parts by weight, preferably from 1 to 20 parts by weight. The obtained ethylene polymer composition may optionally contain an antioxidant, a hydrochloric acid absorber, an anti-aggregation agent, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather stabilizer, an antistatic agent,
Heel additives such as nucleating agents, pigments, and fillers can also be blended. The mixing ratio is appropriate. The core ethylene polymer composition can be prepared according to conventionally known methods.

By blending the low-crystalline ethylene-based random copolymer of the present invention with a crystalline olefin-based polymer other than the other ethylene-based polymer, the durability of molded products made of the crystalline olefin-based polymer can be improved. It is characterized by its impact resistance, especially at low temperatures, and because it contains a low-crystalline core ethylene-based Zindame copolymer, it does not cause a decrease in transparency and surface non-adhesion.

Specifically, the crystalline olefin polymer other than the ethylene polymer includes polypropylene, poly-1-butene,
In addition to poly-4-methyl-1-pentene, poly-1-hexene, etc., propylene/ethylene copolymer, propylene/1-butene copolymer, ■-butene/ethylene copolymer, 1-butene/propylene Like copolymers, α-olefins (al) such as propylene, 1-butene, 1-hexene, ethylene, fluoropylene, l-7'thene,
1-hexene, 4-methyl-1-pentene, 1--1r
The α-olefin (a, Examples include crystalline α-olefin copolymers made of α-olefins (at) which are different from the above. The intrinsic viscosity of the crystalline olefin polymer measured in decalin at 135°C [
η] is usually in the range of 0.5 to 10 dl/y,
The crystallinity is 5% or more, preferably 20% or more.

When the low crystalline ethylene random copolymer of the present invention is blended with the crystalline α-olefin polymer, the blending ratio is usually 0.00 parts by weight per 100 parts by weight of the crystalline α-olefin polymer. The amount is in the range of 30 parts by weight, preferably 5 to 20 parts by weight. The crystalline α-olefin polymer composition may optionally contain an antioxidant, a hydrochloric acid absorbent,
Various additives such as anti-aggregation agents, heat stabilizers, ultraviolet absorbers, lubricants, weather stabilizers, antistatic agents, nucleating agents, pigments, and fillers can also be blended. The nuclear crystalline α-olefin polymer composition can be prepared according to conventionally known methods.

Furthermore, the low-crystalline ethylene random copolymer of the present invention can be blended with various engineering resins to achieve
The physical properties of the engineering resin, such as impact resistance and sliding properties, can be improved, and the inclusion of a low-crystalline ethylene random copolymer does not cause a decrease in transparency and surface non-adhesion. There is. When the engineering resin has a polar group, maleic acid, maleic acid, A modified ethylene-based random copolymer obtained by graft copolymerizing an unsaturated carboxylic acid or its derivative component such as citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, dimethyl maleate, dimethyl citraconate, and dimethyl itaconate. Preference is given to using polymers.

The grafting ratio of the unsaturated dicarboxylic acid or its derivative component is 100% of the low-supply ethylene random copolymer.
It is usually in the range of 0.02 to 50 parts by weight. Specific examples of engineering resins include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as hexamethylene adipamide, octamethylene adipamide, decamethylene adipamide, dodecamethylene adipamide, polycaprolactone, and polyphenylene. Polyarylene oxides such as oxides, polyacetals, ABS, AES1 polycarbonates, etc. can be represented by 91J. The blending ratio of the low-crystalline ethylene random copolymer or its modified product is usually in the range of 0.2 to 20 parts per 100 parts by weight of the engineering resin. The engineering resin composition may contain antioxidants, hydrochloric acid absorbers, anti-aggregation agents, heat stabilizers, ultraviolet absorbers, lubricants,
Various additives such as weathering stabilizers, antistatic agents, nucleating agents, pigments, and fillers can be blended. The resin composition to be engineered can also be prepared according to conventionally known methods.

By blending the low-crystalline ethylene random copolymer of the present invention with various rubbery polymers, the physical properties of the rubbery polymers, such as chemical resistance and rigidity, can be improved. Specifically, the rubbery polymer includes, for example, ethylene/propylene/nonconjugated diene copolymer, ethylene/propylene/nonconjugated diene copolymer,
Examples include 1-butene/nonconjugated diene copolymer, polybutadiene rubber, polyisoprene rubber, and styrene/butadiene/styrene block copolymer.

The blending ratio of the low-crystalline ethylene random copolymer is 1-10 parts by weight per 100 parts by weight of the rubbery polymer.
It is in the range of 0 parts by weight. Various fillers such as a filler, a crosslinking agent, a crosslinking aid, a pigment, and a stabilizer can be added to the rubbery polymer composition as required. The rubbery polymer composition can be prepared according to conventionally known methods.

〔Example〕

Next, the method of the present invention will be specifically explained using examples.

Example ゛1゜100 t/glass flask nitoluene 301+7. fully purged with nitrogen. ! : 2 mmol of bis(cyclopentadienyl)zirconium monochloride monohydride was charged and made into a slurry. Then, 20 mmol of trimethylaluminum (IM solution) diluted with toluene was added dropwise at room temperature. After dropping, the temperature was raised to 60°C and
Allowed time to react. Bis(cyclopentagenyl)zirconium monochloride monohydride was dissolved in toluene and the solution turned dark red. Note that the above reaction was performed with light cut off.

13.95' of magnesium chloride hexahydrate and 125 at of toluene were charged into a 400 d glass flask which had been sufficiently purged with argon, and after cooling to 0°C, 125 at of toluene was added.
250 mmol of trimethylaluminum diluted with M were added dropwise. After dropping, the temperature was raised to 70℃, and at that temperature 9
The reaction was allowed to proceed for 6 hours. After the reaction, solid-liquid separation was performed by filtration, and toluene was further removed from the separated liquid under reduced pressure to obtain methylaluminoxane 7.31 as a white solid. The molecular weight determined by freezing point depression in benzene was 1910, and the m value of the aluminoxane was 31. still,
During polymerization, the aluminoxane was redissolved in toluene.

Using a 2 ton continuous polymerization reactor, 2 ton of purified toluene/
hr, 10 S of methylaluminoxane in terms of aluminum atoms! J gram atom/hr, the zirconium catalyst prepared above was continuously fed at a rate of I x 10-"mi!J gram atom/hr) r in terms of zirconium atom, and ethylene 36
0t/hr, continuously supplied at a rate of 7240t/hr, polymerization temperature 20°C, normal pressure, residence time 0.5 hours,
Polymerization was carried out at a polymer concentration of 36 f/l.

The generated polymer solution is continuously extracted from the polymerization vessel,
Stop the polymerization by adding methanol to the bone,
Furthermore, transfer the po)tumer solution into a large amount of methanol,
The precipitated polymer was dried under reduced pressure at 130°C for 12 hours.

Ethylene bone content 77 weight prefectures, [η] 2.16 dt/?
.

Mw/Mn 1.85, crystallinity 2.1, B value 1. ]
4. Density 0.888 t/cm3, boiling methyl acetate extraction amount 0.31 weight 4? A rubbery polymer of l-4 was obtained. The stress at break and elongation at break of this polymer are each 1
10 kg/an", 900%. The 130-NMR spectrum of the obtained octopus polymer contained αβ, β
No gamma-based signal was observed. The activity per unit zirconium was 7300y~polymer/milligram atom-Zr.

Examples 2 to 8, Comparative Example 1 The polymerization was carried out in exactly the same manner as in Example 1, except that the polymerization was carried out under the conditions shown in Table 1. No signals based on αβ or βγ were observed in the 13 cm NMR spectrum of the obtained polymer. The results are shown in Table 1.

Comparative Example 2 Preparation of Titanium Catalyst 2. 2 tons of tetrabutoxytitanium and 201 grams of anhydrous magnesium chloride were placed in a soo at O8 US porat equipped with a built-in 8 kg SUS ball (I5 φ).
It was ground for 8 hours under nitrogen atmosphere (vibratory mill).

Transfer the co-ground product to 200ml of ethylene dichloride and add 80ml of ethylene dichloride.
Heat at ℃ for 2 hours. Thereafter, the co-pulverized products were separated and washed with n-decane until free titanium tetrachloride was no longer detected. 21 m9 of titanium atoms were supported in the catalyst lt thus obtained.

Using the same polymerization reactor as in Polymerization Example 1, purified Deka 7 wo 2
t/hr, 8 milligram atoms/hr of ethylaluminum sesquichloride in terms of aluminum atoms
The titanium catalyst produced by fA above was continuously fed at a rate of 0.4 μIJ gram atom/hr in terms of titanium atoms, and 300 t/hr of ethylene was simultaneously fed into the polymerization vessel system.
hr, 1-butene was continuously supplied at a rate of 100t/hr, polymerization temperature was 120°C, normal pressure, residence time was 0.5 hours, and polymerization was carried out under conditions such that the polymer concentration was 50 y/l. The subsequent operations were carried out in accordance with Example 1. However, the 130-NMR spectrum of the obtained polymer has
No signals based on αβ or βγ were observed. The results are shown in Table 2.

Comparative Example 3 Purified hexane was purified by passing through the same polymerization reactor as in Example 1.
t/hr ethylaluminum sesquichloride at 1 milligram atom/hr with aluminum atom iA'JE
, vanadyl trichloride is 0.1 miU in terms of vanadium atoms.
Ethylene 200 t/hr, propylene 2
Continuously supplied at a rate of 40 t/hr, polymerization temperature 50
℃, normal pressure, residence time 0.5 hours, polymer temperature 0 degrees 41/
Polymerization was carried out under conditions such that: The subsequent operations were performed in exactly the same manner as in Example 1. IIc-N of the obtained polymer
The MR spectra have αβ, βγ as in Examples 1 to 8.
A signal based on was observed. The results are shown in Table 3.

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

Application Examples 1 to 5 Comparative Application Examples 1 to 6 [Example 2] and ethylene-based random co-mr in the comparison column
Combination and Bolier f L/7 resin (MFR0,44f/1
0 m1n, density 0.959 y/crn3) and 1:9
After melting and mixing at a ratio of
+ to 30? / Melon 2 before 2 pressurization, held for 30 seconds → 20℃ cold press, 50 kg/cm" pressure and held for 3 minutes). Film impact strength and transparency (haze value) at 23℃ and -20℃ for this film The results are shown in Table 4.

Application IIA6 Comparative Application Examples 7 to 9 Ethylene-based random copolymer and polypropylene) I resin (MFR, 109/10 rni
n) and G drama mixed in a ratio of 1:9 1. Tayu, thickness 30μ
A press film was created (same as Application Example 1). The film impact strength and transparency (haze value) at 23°C were measured for this film. The results are shown in Table 5.

Actual test h5s11 The same procedure as in Example 1 was carried out except that tri-n-octyl aluminum was used instead of trimethyl aluminum used in Example 1.

Using the same polymerization reactor as in Polymerization Example 1, purified toluene was
t/hr Methylaluminoxane synthesized in the same manner as in Example 1 was used at a rate of 5 milligrams of serosa/hr in terms of aluminum atoms.
hr, the zirconium catalyst prepared above was continuously fed at a rate of lXl0-'' milligram atoms/hr in terms of zirconium atoms, and ethylene 36 was simultaneously fed into the polymerization vessel.
0t/hr.

Propylene was continuously supplied at a rate of 240 t/hr and 1.4-hexadiene at a rate of 2 t/hr, the polymerization temperature was 20°C, normal pressure, the residence time was 1 hour, and the polymer concentration was 2 at/hr.
Polymerization was carried out under conditions such that: The subsequent operations were performed in exactly the same manner as in Example 1. Ethylene content f >70MN'-
[:'7'] 1.79 dA/f, Mw/Mn 1.9
2. Crystallinity 04. R value 1,19, density 0, 871-
? 7cm", iodine value 9, methyl acetate extraction
A rubber-like polymer of No. 38 m[1 was obtained. In addition, the 13cm NMR spectrum of this polymer shows αβ
, no signal based on βγ was observed in the cutter. The activity per unit of zirconium was 20,009-polymer/milligram atom-Zr.

〔Effect of the invention〕

In summary, the low-crystalline ethylene random copolymer of the present invention has a narrow molecular weight distribution and composition distribution, and has excellent transparency.
The surface is non-stick and has low crystallinity.

The copolymer of the present invention improves the Pi properties of the thermoplastic resin by blending the copolymer with the resin.

1 other person

Claims (1)

[Scope of Claims] 1. A low-crystalline ethylene-based random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, comprising: (a) an ethylene component content of 35 to 85% by weight; range, and the content of α-olefin component is 15 to 6
(b) Intrinsic viscosity measured in decalin at 135°C [η]
is in the range of 0.5 to 10 dl/g, and (c) molecular weight distribution determined by gel permeation chromatography (
@M@w/@M@n) is 25 or less, (d) the crystallinity determined by X-ray diffraction is 30% or less, and (e) the following formula (I) B≡P_O_E/( 2P_O・P_E) (I) [In the formula, P_E represents the molar fraction of the ethylene component in the copolymer, P_O represents the molar fraction of the α-olefin component, and P_O_E represents the total dy
The B value represented by [indicates the molar fraction of α-olefin/ethylene chain in the ad chain] is in a range that satisfies the following formula (II) 1.05≦B≦2 (II), and (f)^1 ^3 In the C-NMR spectrum, αβ and βγ signals based on methylene chains between two adjacent tertiary carbon atoms in the copolymer main chain are not observed, and (g) boiling methyl acetate soluble portion. A low-crystalline ethylene-based random copolymer, characterized in that the amount is 2% by weight or less. 2. In the presence of (A) a zirconium hydride compound having a group having conjugated π electrons as a ligand, and (B) a catalyst consisting of aluminoxane, ethylene and an α-olefin having 3 to 20 carbon atoms are conjugated. (a) The content of the ethylene component is in the range of 35 to 85% by weight, and the content of the α-olefin component is in the range of 15 to 6% by weight.
(b) Intrinsic viscosity measured in decalin at 135°C [η]
is in the range of 0.5 to 10 dl/g, and (c) molecular weight distribution determined by gel permeation chromatography (
@M@w/@M@n) is 2.5 or less, (d) the crystallinity determined by X-ray diffraction is 30% or less, (e) the following formula (I) B≡P_O_E /(2P_O・P_E)(I) [In the formula, P_E represents the molar fraction of the ethylene component in the copolymer, P_O represents the molar fraction of the α-olefin component, and P_O_E represents the molar fraction of the entire dyad chain. Indicates the mole fraction of α-olefin ethylene chains] The B value expressed by the formula (II) below satisfies the following formula (II): 1.05≦B≦2 (II), and (f)^1^3C- In the NMR spectrum, αβ and βγ signals based on methylene linkages between two adjacent tertiary carbon atoms in the copolymer main chain are not observed, and (g) the boiling methyl acetate soluble portion is 2. A method for producing a low-crystalline ethylene-based random copolymer from ethylene and an α-olefin having 3 to 20 carbon atoms, the amount of which is 0% by weight or less. 3. (a) The content of the ethylene component is in the range of 35 to 85% by weight, and the content of the α-olefin component is 15% by weight.
(b) the intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 10 dl/g, and (c) the molecular weight determined by gel permeation chromatography. Distribution (@M@w/@M@n) is 2
．． 5 or less, (d) the crystallinity determined by X-ray diffraction is 30% or less, (e) the following formula (I) B≡P_O_E/(2P_O・P_E) (I) [in the formula, P_E indicates the mole fraction of the ethylene component in the copolymer, P_O indicates the mole fraction of the α-olefin component, and P_O_E indicates the mole fraction of the α-olefin/ethylene chain in all dyad chains.] The B value expressed by is in a range that satisfies the following formula (II): 1.05≦B≦2 (II), and (f)^1^3C-NMR spectrum shows that αβ and βγ signals based on methylene chains between two adjacent tertiary carbon atoms are not observed, and (g) the boiling methyl acetate soluble portion is 2.0 weight or less;
A compounding agent for thermoplastic resins comprising a low-crystalline ethylene-based random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.