JPS5811512A - Ethylenic copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to ethylene copolymers. More specifically,
This invention relates to an ethylene copolymer that has excellent impact resistance, environmental cracking resistance, and moldability.

Density 0. The higher the average molecular weight of so-called high-density polyethylene, the higher the average molecular weight, the higher the performance of the high-density polyethylene.Among these, impact resistance, environmental cracking resistance, etc. are significantly improved in the high molecular weight range.

Also, as a way to bring out the characteristics of Towara.

It is also generally known to copolymerize ethylene with other alpha-olefins. The α-olefin used in this case generally has 3 to 2 carbon atoms, and the more α-olefins with a higher number of primes are copolymerized, the more the effect of improving the carbon content increases. By copolymerizing ~1 α-olefins, the melt index is Q, 07 ~ 0.627
10 minutes, the density is 0.9 da 0~0. Zoro 0 f/e(
J and outflow ratio! It has been found that when a polymer having a σ of 200 is used, it becomes an extremely useful ethylene polymer that has the above-mentioned features, leading to the present invention.

What is the gist of the invention? -~? 9.9 weight of ethylene and σ
, /−′−/number of carbons in weight%! A copolymer with ~1 a-olefins, with a melt index of 0.07
The ethylene copolymer has an outflow ratio of tθ to 0Q at ~OAf/10 minutes.

Therefore, the melt index (abbreviated as Mx) is M8'
Based on rMD-/koJ/@/? t) C, ko, /6 It is a dead value when measured under a load. Outflow ratio (abbreviated as νR) is A8
TeMD-/Ko3! In a melt index device based on
This is the value calculated by the outflow ratio (10"/10") at 0" dyne/it. The density is.

The value is measured at 20C by BTMD-/S0S.

The ethylene copolymer of the present invention has etele y and carbon number t A
-/J random copolymer with α-olefin,
The ethylene unit in the copolymer is J~9, preferably 4 by weight! ~Footer? The α-olefin unit with carbon number is 0.1-1% by weight.
The weight is -. Carbon number! -1 α-olefins include pentene-1, hexene-7, octene-1
, decene-I, Hiro-methylpentene-I, and the like. Melt index is 0.01~t), 4f/10min preferably o, ocol 0.11710min in seconds, density is θ, 9hi~0.96t/00 preferably 0. De0
~9 ahead! y/cc, the outflow ratio is to~J0
σ is preferably 60 to too.

One way to improve impact resistance and environmental cracking resistance is to increase the average molecular weight, but if the melt index is too low, that is, if the molecular weight is too high, the melt viscosity will increase too much and the moldability will be extremely poor. Deteriorate. Therefore, the melt index needs to be within the above range.

t+, as mentioned above, it is common practice to copolymerize α-olefin and ethylene to improve the above performance, but the number of carbon atoms in this σ-olefin! -12 carbon atoms than when using α-olefins having 3 to 91 carbon atoms.

The above performance improvements can be obtained with a high density, ie a high stiffness modulus. Also, the outflow ratio! 0~Jσσ
By doing so, the sturdiness is improved.

Therefore, the effects of each of the above ranges of the present invention influence each other, and the ethylene polymer of the present invention has a balance in impact resistance, environmental stress cracking resistance, VT, and WI properties, and also has rigidity. It is extremely useful as it has a high value.

The ethylene polymer of the present invention works effectively as a polymer for large-sized or medium-sized vinyl and has the above-mentioned properties.
In addition, the bow's fissure strength is extremely high.

When producing the ethylene copolymer of the present invention, a so-called Ziegler type catalyst is often used, and in particular, a catalyst system consisting of a solid component containing magnesium, titanium, and a halogen and an organoaluminum compound is used. preferable. Examples of such solid components include the reaction product between an oxygen-containing organic compound of beak magnesium and a titanium halide compound, or a reaction product of an oxygen-containing organic compound of magnesium, an oxygen-containing organic compound of titanium, and an aluminum halide compound. Examples include reaction products such as those obtained by contacting magnesium chloride or its electron donor-treated product with a halogenated titanium compound.

f Ethylene and carbon number using the above M medium system! ~/-a
- For copolymerization with olefins, generally known ethylene polymerization methods are used; (b) In one of the first and second reaction zones, the molar ratio to ethylene in the gas phase is 0.
07~θ, viscosity average molecular weight after polymerization in the presence of hydrogen
00,000 to 700,000 polymers, JO3i of the total polymer production amount
li% to 70% by weight and polymerized in the presence of hydrogen in the other zone in a molar ratio of /J'-70 to ethylene in the gas phase to obtain the ethylene copolymer,
This is one of the preferred methods.

Next, the present invention will be explained in detail with reference to examples, but the present invention is not limited to the examples given below, which do not go beyond the gist of the invention.

In addition, in the following examples, the enjoyment test is as follows.

The obtained polymer product was transferred to a 30mm diameter, Vn-koku, Dalmage screw extruder (a Or, p, m2, temperature C, W/
607:, O, W/ 107::, px/? Oc)
The wires were cross-wired, pelletized, and measured using six samples.

The amount of extrusion molding is determined by Prabender J.
/ D l! Single 111111F output II (0 diameter / 9
．． t mad.

II/D; 1. Fully fried screw with compression ratio = 3, the die is a circular die with a diameter of 0 and a clearance of □J■. The extrusion amount was measured at 0 revolutions/min, and the extrusion amount was divided by the number of revolutions (110 revolutions/min) to obtain the amount of extrusion in grams per number of revolutions. Environmental crack resistance (1BOR-7) d, A8TM
It was measured by the Bell telephone method described in D-/693.

Out of 10 test pieces! The pieces are displayed in time to break.

Is the tensile impact strength MU8? MD-/IKokoko IIK, look for it.

The strength of the film was tested according to the Elmendorf tear strength aJIBP♂116° dirt drop impact tester MD-170.

It was molded using the Kowara film inflation molding method.

The a-olefin content was determined using an infrared spectrophotometer.

Example-7! Danesium jethylate coat mmoz, titanium tri-n-butoxy chloride 10 mmoz, zirconium tri-n-butoxy chloride 2. Summo4
were mixed and stirred at /30c for feeding time. Cool to room temperature, add benzene, then add 6tcK and add ethyl aluminum dichloride J/J! II! ll0j
was dripped. After stirring for 20σf, the precipitate was washed with normal hequinane to obtain a solid component. ! Autoclave kn-hexene-7200f and hexene-7200f
Compound the solid component 1 above! I installed ow9. After heating to roc and introducing an appropriate amount of hydrogen, triethylalkenium 0. ／Press ethylene together with mmot to reduce the total pressure／
! Ethylene was added to maintain kg/ctl and polymerization was continued for 3 hours. During this time, the amount of hydrogen introduced is determined so that the molar ratio of hydrogen to ethylene in the gas phase is 87JK. The obtained polymeric ivy bait f is used = = o, otot7to minutes, PR
==2? It was an ethylene/hexene-7 copolymer having a density of 12.9 feed t/cc and containing 2.1% by weight of hexene-1.

This copolymer was inflation molded to form a 70 μ film, and the Elmendorf tear strength in the longitudinal direction was /J, /k.
l/cIm, lateral direction/0 hirokl/as, dart four-lobed impact atof.

Comparative Example 1 Polymerization was carried out in exactly the same manner as in Example 1 except that fiK butene-7601 was used instead of hexene-1 20σf. The nine polymers obtained are /, 0 / O
M engineering at f = 0.0 hiro I f / 70 minutes, 'IRg7J
, density O, dedade f/ca and butene-1/, 1 weight-
It was an ethylene-butene-I copolymer containing h. ,・
The polymer copolymer was inflation molded in the same manner as in Example 1, and the film strength was measured.
g/51. It was a dirt drop impact 301f.

Examples-2 to 10 and Comparative Examples-2 to 3 (1) Production of solid component (a) Magnesium diethoxide oynmot
Add KVQ titanium chloride Jtommot/2 at 30C
Stir for hours. Thereafter, the precipitate was washed with n-hexane to obtain a solid component.

(b) Magnesium diethoxide
K titanium tri-normal butoxy chloride / Owlm
ot and (i normal butyl alcohol / o mmo
The mixture was stirred at 0C for 2 hours. At room temperature, add benzene l group OCC to make a homogeneous solution. Next OCK Ether Aluminum Sesquicuride / / 01111
0t was added. The resulting precipitate was washed with h-hexane at room temperature to obtain solid component (13).

(2) Polymerization of ethylene and a-olefin! N-hexano Jt and a predetermined amount of the solid component (&) or (1)) are placed in an autoclave. Next, various α shown in Table-1
- A predetermined amount of olefin is introduced, and hydrogen is introduced so that the molar ratio of hydrogen to ethylene in the gas phase (H/1) is 1 as shown in Table 1. Next, the temperature was raised to T and K shown in Table 1, and ethylene was injected together with the specified amount of organoaluminum compound shown in Table 1, and the total pressure was adjusted to the nine values P shown in Table 1. Additional ethylene was introduced to maintain the

Table-/After the polymers of Y and f are produced.

Immediately the temperature T shown in Table-7! At the same time, the molar ratio of hydrogen and ethylene in the gas phase was adjusted to be (H/[!i)1, and the total pressure was set to '*'y/cd.

At the same time, α-olefin was added in the amount shown in Table 1. P! Polymerization was stopped when the total amount of polymer produced reached Y while adding ethylene to maintain Y, and after drying, the pellets were formed and various physical properties were measured, and the results shown in Table 1 were obtained.

In comparison, the dirt drop impact of the Elmendorf tear embryo is significantly inferior, and although the density drop impact is lower than that of the actual example 3, Patent Applicant Mitsubishi Chemical Industries, Ltd.

Claims (1)

[Claims] rl) 92 to 99.9 weight-1! i: ethylene and o,
t-/number of carbons in weight ti! A copolymer with an α-olefin of ~lλ, the melt index is 0.0/~θ,
Ethylene copolymer (2) having an outflow ratio of to to -00 at 6 f/10 min. Ethylene copolymer according to claim 1 having a density of 0.9 da to O1 4 y/cc. union