JPS58122908A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To produce a polyolefin markedly excellent in impact resistance and moldability as well, by conducting copolymerization of ethylene with other alpha- olefins in two stages in the presence of a specified catalyst under specified conditions. CONSTITUTION:Two-stage copolymerization of ethylene with other alpha-olefins is conducted by organic slurry polymerization in the presence of a catalyst system comprising a compound of a transition metal such as Mg or Ti and an organoaluminum compound under the following conditions: i.e., the reaction mixture obtained by polymerization in the 1st reaction zone is further polymerized in the 2nd reaction zone; a copolymer A, viscosity-average MW 150,000-700,000, is produced in the 1st zone in a yield of 70-30wt%, and a copolymer B, viscosity- average MW 10,000-30,000, is produced in the 2nd zone in 70-30wt%; the ratio between the viscosity-average MW's of copolymer A and B is 5-55; and a copolymer, melt index 0.01-0.4g/10min and density 0.91-0.94g/cm<3>, is finally obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyolefin having excellent impact resistance and moldability.

In recent years, in the field of polyolefin films, much research has been done on improving the impact strength of polyolefins with the aim of making films thinner, and as a result, the current focus is on low melt index, low density polyethylene, which is used for applications called ultra-thin films. , or linear low-density polyethylene, etc., there is a growing demand for thinner polyolefin films with improved impact strength to some extent. #The development of polyolefins with improved impact strength has been desired.

31 In view of the above-mentioned current situation, the present inventors have conducted extensive studies, and as a result, have succeeded in copolymerizing ethylene and other α-olefins in one step using a specific catalyst and under specific conditions. It was discovered that by carrying out this process, a polyolefin having significantly superior impact resistance and moldability compared to conventional polyolefins could be obtained, and the present invention was achieved based on this finding.

That is, the gist of the present invention is to copolymerize ethylene with other α-olefins in a hydrocarbon solvent under slurry conditions using a catalyst thread consisting of a transition metal compound component and an organoaluminum compound. , a solid catalyst component containing a magnesium compound and a titanium compound is used as a transition metal compound component, and (a) the polymerization reaction is carried out in one step, that is, the reaction mixture obtained by combining in the first reaction zone is transferred to the first reaction zone. (o) In either of the first and first reaction zones, the molar ratio to ethylene in the gas phase is 0.
00/-0,! In the presence of hydrogen, the molar ratio to ethylene in the liquid phase is 0.1 A;~/1 carbon number q~/,
By copolymerizing ethylene and α-olefin, co-polymerizing ethylene and α-olefin, a viscosity average molecular t/J of 700,000 to 700,000, a density of 0.900 to 0.94 tO, and a shoulder co-electrolyte A is produced by combining whole blood. 30 hit% to 70% by weight of the amount, and in the other zone O,S-
In the presence of t of hydrogen, copolymerize ethylene and α-olefin by copolymerizing ethylene and α-olefin with a molar ratio of 1 to 30 carbons to ethylene in the liquid phase to obtain a viscosity average molecular weight of 70,000. ~S force, density 0.90! r〜0.9 j j
Copolymer B with lI/d was produced in an amount of 7θ to 30% by weight of the total polymer production, and further, (viscosity average molecular weight of electropolymer A/(
The viscosity average molecular weight of the polymer B is −jj, and the melt index of the final polymer is 0. Oi -0,'l fi / / Omin A method for polymerizing olefins characterized by setting the density to 0.9 /θ to 0.9 IIO&Af.

To explain the present invention in more detail, the catalyst thread used in the present invention is a catalyst system consisting of a solid catalyst component containing a magnesium compound and a titanium compound as transition metal compound components, and an organoaluminum compound.

By carrying out polymerization using these catalyst systems under the polymerization conditions described below, a polymer having high impact strength and excellent moldability can be obtained with good slurry properties and high productivity.

Examples of the homogeneous catalyst component containing a magnesium compound and a titanium compound include the following solid catalyst components of (al to (f+).

(a) A hydrocarbon-insoluble solid product obtained from a reaction mixture of a solid complex consisting of a magnesium halide, a titanium halide and an electron donor, and an organoaluminium compound. (b) An oxygen-containing organic compound of magnesium and an oxygen-containing organic compound of titanium. Reaction products between compounds and aluminum halogen compounds (cl Reaction products between oxygen-containing organic compounds of magnesium and oxygen-containing organic compounds of titanium and halogen compounds (al) Reaction products between oxygen-containing organic compounds of magnesium and titanium halogen compounds Reaction product (θ) A reaction product obtained by contacting a titanium compound with a solid reaction product of boron alcolade and a Grignard reagent (f+ obtained by treating a magnesium-containing solid boron with an oxygen-containing organic compound) Preferable examples of the magnesium compound which forms a solid include magnesium dihalide, magnesium trichloride, allyloxymagnesium, alkoxymagnesium halide, and Grignard reagent.

Further, as the titanium compound, trivalent or tetravalent titanium halides, alkoxytitanium, γ-alkoxyhalokenated titanium, etc. are preferable.

As the aluminum halogen compound, al=7-kylaluminum dichloride, alkylaluminum sesquichloride, dialkylaluminum monochloride, etc. are preferable.

As the silicon ice halide, silicon tetrahalide, silicon alkyl trihalide, silicon allyl trihalide, silicon dialkyl dihalide, etc. are used.

As the boron compound, boron alcoholade or halogenated boron alcoholade is used.

Further, as the electron donor used for the solid catalyst component (al), ether, carboxylic acid ester, alcohol, amine, etc. are used.

The solid catalyst components (al to (f)) are prepared using the raw materials as mentioned above.
Knee Tokukai Sho S Fuichi 61g 06, Tokugan Shoj5-4zayzag5 Tokukai Sho! Preferably, the methods described in Japanese Patent Application No. 5S-ITXT COS, Japanese Patent Application Laid-Open No. 1982-6 Tag θ, etc. are suitable.

Among these solid catalyst components, the use of (al) solid catalyst components is particularly preferred.

8- (To explain the solid catalyst component of al in more detail,
(General formula % formula % () which is a raw material when producing 11M1 solid catalyst component of al
, n, 'p are as mentioned above. As the solid complex represented by ], a compound in which Xl and x2 are chlorine atoms, D is an ether, and n is O is particularly preferred. D is 1 below. Examples of the child donor compound include those exemplified as R1 in the general formula of the halogen-containing compound of titanium described below, which are deposited from an electron donor compound solution of magnesium chloride and a halogen-containing compound of titanium. By doing so, it is possible to perform fAIR. Here, the magnesium halide has the general formula [where xi represents a halogen atom]. ] is used.

Specific examples include anhydrous magnesium chloride, anhydrous magnesium bromide, and anhydrous magnesium iodide. Among them, anhydrous magnesium chloride is preferred.

On the other hand, as a titanium 7.logen-containing compound, the general formula % formula %) [formula, in which X2 is).
n represents a number in the range of θ to l, m +
n is a number that matches the valence of titanium. ]
is used. Specifically, titanium tetrachloride, titanium trichloride, titanium tetrabromide, titanium tribromide, titanium tetraiodide, titanium Misawa, titanium tetrafluoride, titanium trifluoride, monoethoxytrichlortitanium, monogloboxytrichlor. Examples include titanium, monobutoxytrichlorotitanium, and the like. Among them, titanium tetrachloride and titanium trichloride are preferred.

Next, specific examples of electron donor compounds include aliphatic ethers such as diethyl ether and dibutyl ether, cyclic ethers such as tetrahydrofuran and tetrahydrobyran,
Examples include carboxylic acid esters such as ethyl acetate and ethyl benzoate, alcohols such as ethanol and butanol, and amines such as pyridine, among which tetrahydrofuran is preferred.

To prepare a solid complex, after mixing all of the above halogen-containing compounds of maggotide, siaum and titanium in an appropriate ratio, add an excess of the electron donor compound and heat the mixture at a temperature ranging from 0°C to the boiling point of the electron donor compound. A method in which the electron donor compound is reacted to form a complex to obtain a solution of the electron donor compound, and then the solution is cooled and crystallized, a method in which the electron donor compound is distilled off by evaporation,
Alternatively, it may be co-precipitated by adding a poor solvent such as a hydrocarbon.

Another method is to separately synthesize an electron donor compound complex of a red sea bream, a sium electron donor compound complex, and a titanium 7. After mixing and dissolving, a solid complex can also be obtained by co-precipitating by the method described above.

The ratio of magnesium halide to the halogen-containing compound of titanium is in the range of 0 to 100 in terms of Mg/Ti (atomic ratio). If this value is outside the above range, the polymerization activity of the resulting catalyst will be insufficient.

Next, in a solid complex hydrocarbon solvent produced by the above method, a compound of the general formula [where u2 represents an alkyl group, an aryl group, or a cycloalkyl group, X3 represents a...logon atom, and q represents 1 to
It is a number in the range of 3. ] is reacted with an organoaluminum compound represented by Specific examples of the organoaluminum compounds used here include ethylaluminum dichloride, ethylaluminum seschloride, diethylaluminum 12-miniram monochloride, triethylaluminum, triisobutylaluminum, etc. Among them, ethylaluminum dichlorite, ethylaluminum Aluminum sesquichloride, diethylaluminium monochloride is preferably used in the temperature range of t s °C. Hydrocarbon solvents used include aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene and toluene. Particularly preferred is a solvent in which a reaction product of an electron donor compound and an organoaluminum compound, which is produced as a by-product during the reaction, is soluble.

Regarding the indigo used in the organoaluminum compound used, the molar ratio is θ in the ratio of the electron donor compound to I in the solid complex, /<organoatubenium compound/electron donor compound<
i.

Preferably, an amount of 0.3% organoaluminum compound/electron donor compound is used.

A solid insoluble in the hydrocarbon solvent is thus obtained, and this solid is separated from the by-product reaction product of the organoaluminum compound and the electron donor compound. in particular,
The solid may be separated from the reaction mixture by filtration, decantation, etc. and then washed with an inert hydrocarbon solvent, or an inert carbonated water ice solvent may be added to the reaction mixture to perform the washing treatment and separation at the same time.

As the inert hydrocarbon solvent used here, the inert hydrocarbon solvent used previously in the reaction of the solid complex and the organoaluminum compound is used.

The remaining amount of the electron donor compound component in the hydrocarbon-insoluble solid catalyst component obtained by this operation is determined by the molar ratio of the electron donor compound and the sum of magnesium atoms and titanium atoms. Ti) < /.

By using the solid catalyst component (a) as described above, an olefin copolymer with high impact resistance and excellent moldability can be produced.
It has the advantage that it is particularly easy to manufacture slurry with good properties and high productivity.

Next, as an organoaluminum compound used as a cocatalyst, for example, the general formula [where RB represents an alkyl group, an aryl group, or a cycloalkyl group, X' represents a halogen atom, and r represents a
It is 3. ] Examples include organoaluminum compounds represented by the following.

Specifically, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride Liao,
Examples include ethylaluminum sesquichloride.

These organoaluminum compounds can also be used as a mixture as appropriate.

The ratio of the hydrocarbon-insoluble solid catalyst component to the in-house aluminum 15-ram compound is usually 0.00% in terms of Al/Ti atomic ratio. /~100--preferably used within the range of lA-coO.

In the present invention, copolymerization of ethylene and other α-olefins is carried out using the above-mentioned catalyst system under conditions of slurry polymerization in a hydrocarbon solvent, that is, at a temperature of aO<0>C to lOO<0>C. As the hydrocarbon solvent, aliphatic hydrocarbons such as propane, butane, pentane, hexane, etc., alicyclic hydrocarbons such as cyclohexane, etc. are used, but use of butane is particularly preferred.

Other α-olefins that are copolymerization components have 4 carbon atoms.
! -t, 2 α-olefins, for example,
Examples include butene-7, hexene-/octene-1, and the like.

The content of the copolymer component is usually 2 to 50% by weight in the copolymer.
Preferably! -/! It is wt%.

Therefore, in the present invention, the polymerization reaction is carried out under the following conditions (a), (b), and (c).

(a) The polymerization reaction is carried out in one step, that is, the reaction mixture obtained by polymerization in the first reaction zone is further polymerized at a certain zone pressure of the first reaction zone, and (b) the reaction mixture obtained by polymerization in the first reaction zone is further polymerized. One reaction zone has a molar ratio of 0-00 to ethylene in the gas phase in one zone.
/ -0.3 molar ratio to ethylene in the liquid phase in the presence of hydrogen. /! r~/, l carbon number q~l α-
By copolymerizing ethylene and α-olefin with olefin coexisting, the viscosity average molecular weight is ~7θ million, density o, q
Copolymer A of oθ~0.9 Q Ok- was produced at 30% by weight to 70Mflk% of the combined lid of all cars, and 1112
o in the molar ratio to ethylene in the gas phase in one zone.
, r - t, in the presence of hydrogen in the liquid phase, ethylene and α-olefin are copolymerized by copolymerizing an α-olefin with a molar ratio of carbon number q~/2 of /~Jθ to ethylene in the liquid phase to reduce the viscosity. Average molecular weight 10,000 to 50,000, density o, q o s ~ o, q
Copolymer B of s s g/d was added to 70% of the total polymer production amount.
~30 weight i% is produced, and further ('viscosity average molecule i of IM coalescence A)/()m viscosity average molecule 1゛ of coalescence B) is jS
-jj, (c) The melt index of the blood mixture that is finally formed is 0.0/~O2 p//θ, and the density is 0.9/
0 to 0.91θg shoulder.

These (a), (b), e-1? To explain the conditions, the λ-stage gold production in (a) can be carried out either by a continuous polymerization method or by a batch polymerization method. In the case of continuous polymerization, the reactors are connected in a λ group series, and the reaction mixture obtained by combining in the first reactor is introduced into the first reactor to continue the reaction. The mixture is then reacted sequentially in seven reactors equipped with the same method.

Among these, continuous polymerization is preferred.

According to the reaction conditions (b), first, in one of the first and first reaction zones, hydrogen is present in a molar ratio of 0.0θl to U,j to ethylene in the gas phase. With respect to ethylene in the phase, α-olefins having a carbon number of 0.1 to 1 to 1.2 coexist, and the α-olefins are co-contaminated, and finally The lIi support A is produced in an amount of 3θ heavy weight % to θ2 weight % of the total production amount of all the produced polymers, and the viscosity average molecular weight of the polymer A obtained here is set to be ljf 10,000 to 7θ 0,000.

The viscosity average molecular weight is determined by measuring the intrinsic viscosity in a tetralin solution at 730°C, and calculating [η] - θX / 0' x M0°
7211 ([η) is the intrinsic viscosity, and M is the value calculated from the formula for the viscosity average molecular weight. ) when the locking body A is produced in the first reaction zone with the presence of polymer B loaded in the first reaction zone;
The viscosity average molecular weight of polymer A is expressed by the following formula, [η'J, -(100[ηJ-W'B[η]B,)/W
A (where [η] represents the intrinsic viscosity of the polymer, and [η
] B indicates the limiting viscosity of polymer B, [η] indicates the limiting viscosity of the entire polymer obtained as 1a in the first reaction zone,
WA is fflt% of the stopper A produced in the first reaction zone
The viscosity average molecular weight can be calculated by determining [η]A from the equation (where WB is the percentage of charge of the polymer B produced in the first reaction zone 19).

However, if the viscosity average molecular weight is less than 150,000, the resulting blood coalescence (i & the impact strength of the ultimately produced total polymer 1) will be low, and if it exceeds 70,000, the moldability will be undesirable. The preferable range is from 0,000 to 600,000, particularly preferably from 300,000 to zO.

The molar ratio of hydrogen to ethylene in the gas phase is 0.001
In Miran, the viscosity average molecular weight often exceeds 700,000,
If it exceeds O or S, the viscosity average molecular weight will often be less than /j0,000, which is not preferable.

This is a value measured from

Blood coalescence A is produced in the first reaction zone in the presence of polymer B produced in the first reaction zone. , /:l indicates the density of the total polymer produced in the first reaction zone, and WA, WB・, W# are the charge storage % of the total polymer A, B%, respectively. You can ask for a sword from ).

However, if the density is o, q o o gZgoheman,
When the obtained polymer (all the polymers finally produced) is used as a film, problems such as stickiness, blocking, or insufficient rigidity of the film occur, which is not preferable. Moreover, if the density exceeds 0.941°g/cd, the impact strength will be insufficient, which is not preferable.

The molar ratio of α-olefin to ethylene in the liquid phase is o
, lz* droplets, the density often exceeds 0.9'IO, and if it exceeds /, the density often falls below 0.900, which is not preferable. If Form 1 is less than 30% by weight or exceeds 70% by weight, moldability will be lowered, which is not preferred. The preferred range is 3θ*i% to 1-0**%, especially 33 times before % direct reaction beam θ℃ to loθ℃, 10
From 9 to 10 o'clock nA, the sum of the partial pressures of ethylene, hydrogen and α-olefin is R1' or 0. ! 'P/i gauge~i o o
It may be carried out under h/crd pressure.

Then, in the other reaction zone, polymerization is carried out in the presence of hydrogen in a molar ratio of 0.3 to ethylene to ethylene in the gas phase,
Viscosity average molecular weight 10,000 ~ left banko wife gong≠→→ka→NEET j4
Tsukuda's polymer B is produced in an amount of 70% to 30% by weight of the total amount of the blood mixture to be finally produced. viscosity average molecular weight,
The density is a value determined by the method described above.

When polymer B is produced in the first reaction zone in the presence of polymer A produced in the first reaction zone K), the viscosity average molecular cap of blood aggregate B is expressed by the following formula % formula % ( In the formula, [η] represents the intrinsic viscosity of polymer B, and [η]
A indicates the limiting viscosity of the polymer A, and [η] indicates the limiting viscosity of the entire final polymer obtained in the first reaction zone. Throat indicates the type of polymer A obtained in the first reaction zone. Indicates the open%,
W- indicates the percentage of polymerization of polymer B obtained in the first reaction zone). All you have to do is calculate.

However, if the viscosity average molecular weight is less than 7, the impact strength of the resulting polymer (the entire polymer finally produced) will decrease, and if it exceeds 10,000, the moldability will decrease, which is not preferable.

When the molar ratio to ethylene in the gas phase is less than θ, the viscosity average molecular weight of polymer B often exceeds 3,
If it exceeds S, it is often less than 10,000, which is not preferable.

The preferred range is 7. When polymer B is produced in the first reaction zone in the presence of the electropolymer produced in the seventh reaction zone, the density of polymer B is calculated by the following formula (where the base is the density of blood coalesce B). , b indicates the density of the polymerized 23 monomer A, J indicates the density of the total polymer produced in the first reaction zone, wA', wnjw are each polymerized, and
When using a polymer (finally produced polymer) with a density of less than 17.4 as a film, problems such as stickiness, blocking, and insufficient rigidity of the film occur, which is not preferable. . Also, the density is o, 't
If it exceeds r, the impact strength will be insufficient, which is not preferable.

The molar ratio of α-olefin to ethylene in the liquid phase is 7.
If the density is less than 0. Q! ;! It often exceeds I/cII, and when it exceeds 30, the density often becomes less than 0.901, which is not preferable.

If the amount produced is more than 70% by weight or less than 30% by weight, the moldability will be low, which is not preferable. The preferred range is 70 Arashi i%~Qo car 1%, especially 6S weight%~+1 Ekiw%.
It is.

The polymerization reaction may be carried out under the same polymerization time and pressure conditions as for the polymer A described above.

24- may be used, but preferably the density of the polymer produced in the first reaction zone is greater than or equal to the density of the monopolymer produced in the first reaction zone. By performing polymerization in this order, even when producing a low-density polymer (the final product),
It has a high bulk density, good slurry properties, and can obtain a blood mixture with high productivity.

(Viscosity average molecule t of polymer A)/(viscosity average molecule t of blood coalescence B) is j~11. Preferably /θ~g0. If this ratio is less than 3, the moldability will decrease, and if it exceeds J, the impact strength will decrease, which is not preferable.

Therefore, the melt index of the entire polymer finally produced according to the conditions of (2), ie, the mixture of polymer A and polymer B, is O2θ/~o, yy7io. Here, the melt index is based on ASTM D −/2 J g, 100°C, λ,
The unit is 9/10 minutes, measured under 169 degrees.

If it exceeds o, ti, the impact strength of the entire polymer finally produced will not be significantly high, which is not preferable.

If the melt intex is less than 0.0/2, moldability decreases, which is not preferable.

It is preferable that the polymer produced as described above is first kneaded.

The polymer obtained by the present invention is homogenized,
It can be made uniform by continuous kneading using a single screw extruder or the like. The polymer obtained after cross-talk has the advantage of having no fish eyes.

Next, the present invention will be explained in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

In addition, in the following examples, physical property tests were carried out using the obtained polymer powder in a 3θ fin summer, L, /D = core, Dalmage screw extruder (4 tOr-pm, temperature o, = it
0°C, a2 = igo°C, D = t9θ°C) and measured using a bulleted Zambre.

The amount of extrusion molding as a measure of moldability was determined using Brabender's 2/DQ single screw extruder ("1 diameter/9./0, T,/D
= , 2 / , full-flight screw with compression ratio = 3, the die has an IK diameter of 20 M JJ and a clearance of 0. S
Depending on the fin circular die), the die temperature is 20θ℃ / rotation speed /
The extrusion rate was measured at 0 revolutions per minute to the left (-), and the extrusion amount was divided by the number of revolutions (lso revolutions per minute) to obtain the molding mass per revolution. Judgment was made visually from the extrudate.

Falling weight impact strength as film strength is ASTM-D-
Measured based on t 709. However, here, the falling weight was set as θ.

The film was manufactured by the blown film method under the following conditions.

Molding die: 3θmg circular die, clearance c,
2III+ Temperature: C1, C2, C, die head, die all 30℃ 27- Rotation speed: lOorpm Frost line: Cocm Blow-up ratio: Cofilm thickness: l/lott Melt index cold (abbreviated as M process) is ASTMD −
Measured at 100° C. and directly under −J69 load based on 3 g K. Outflow ratio (abbreviated as PR) is ASTM D-123g
K-based melt index device.

, the shear force value is 10'dynθ/d and lθ5a3
'ns/crl outflow ratio (M engineering 106/
MX, o, ).

The solid catalyst components used in the Examples and Comparative Examples are any of the following (F), (B) and (0).

9bl (A) Magnesium ethoxide/l was homogenized with 01ml. Next, lower stubbenzene was added to the mixture until the temperature reached 60°C to form a homogeneous solution.

Next, JL (17!, 01nJr1o1) of ethylaluminum sesquichloride was added dropwise at a predetermined temperature and stirred for 1 hour. The catalyst component was obtained by washing the generated precipitate with n-bexane.

A portion of the obtained solid is dried to form a powder.

This powder contains Mg/1. Offfi amount%, T1Kio
, s weight i%.

(B) (Il hlg 01□' JJ THF (
Using a Q-manufactured Soxhlet extractor, commercially available bulk anhydrous MgO12/01 dehydrated and deoxygenated tetrahydrofuran (hereinafter abbreviated as lTH'B) was extracted under an atmosphere of electric bed scum.
A reflux extraction operation was performed using the o door. After about 20 hours, Mg
Almost no o12 solids were observed. This extract was concentrated to about 1/2 ml, allowed to cool to room temperature, and then dried under a stream of dry nitrogen gas to obtain a white powder solid. The chemical analysis values (car 1-%) of the obtained solid were as follows.

Mg O], CH analysis value /l/3 t333 MUY calculation, T% / 廁') /-ρ 3j
G s9 (b) Ti1l, -? THF
Using a sock 1 no extractor, 6 g of nitrogen gas T7 and I atmosphere tube τ'ol, reduced with hydrogen, was extracted under reflux from dehydrated and deoxygenated TklFJOOmlK. About 70 hours 1Tio1s is almost dissolved and THF
The phase turned a deep brown color. By cooling this day and night, blue li'+1 body crystals were precipitated, and N-made n
- Washed with hexane and dried under a stream of iMX gas at room temperature to obtain a sky blue solid powder. This is recrystallized once using purified Tl (II'), and the analytical value (Mi'M%) of the obtained solid is shown as the analytical value.
1.21 Kog41 "calculation value (Till, ・, 1
(as THF) 110 2 g, 7 (c) Production of solid catalyst component MgO synthesized in Production Example 0) in a flask pre-prepared with a base material 1t ・IA; TH: F / j , km
Prepare mol. Then dehumidified and deoxidized THF/1 m
When 1 is injected, the MgO1t-IJ THF powder immediately dissolves to form a colorless homogeneous solution.

Similarly, in another flask, the TiC synthesized in Production Example (b)
! 1. −． 7. Prepare 33 mmol of THE'/.

Next, 7 ml of dehumidified and deoxygenated THF is injected to form a purple-brown homogeneous solution.

Next, both of the above bath solutions are mixed and reacted at 60° C. for 1 hour.

After the reaction, the above solution was diluted with purified n-hexane lθ at room temperature.
θml was slowly and thoroughly washed with purified normal hexane over 7 hours to obtain a normal hexane slurry. (Mg+T1) in the slurry at this time (114 degrees is 0..3
It was mol/l.

To this n-hexane slurry was added diethylaluminum chloride/2.1 mmol under stirring at y-o°C.
was added dropwise and reacted at A and t'C for 1 hour.

31- After cooling, the solid catalyst components u and jp were obtained by washing with n-hexane.

The T1 content in the solid catalyst component was 1/lii%.

(3 m
O], //added in the form of a n-butyl ether solution. After the addition, the mixture was stirred at the highest temperature for 7 hours, and the resulting solid was washed with n-hexane.

The solid co obtained above! Titanium tetrachloride octopus at room temperature in rog,! ml, the temperature was raised to 1-0°C, and the mixture was stirred at 710°C for 1 hour. Using the apparatus, extract the liquid from the top 5, then add titanium tetrachloride (tml) again, repeat the above operation, wash the obtained product with n-hexane, and polymerize in the form of n-hexane slurry. provided.

32-Example/-j and Comparative Example/-, 2!7 stainless autotra 1 knob, butane, 2. ,? 1. / -4
xene, and cocatalyst triethylaluminum θ, j 6
Charge mmol and raise the temperature to 30°C.

After raising the temperature, hydrogen was introduced and the solid 11+14 medium components shown in Table 7 were obtained. R4 is introduced together with ethylene to initiate polymerization. Table - / shows (H!/ethylene) gas phase molar ratio and (l-
(hexene/ethylene/ethyl) indicates the liquid phase molar ratio.

As the polymerization progresses, absorption of ethylene is observed, but additional ethylene is introduced to keep the total pressure constant. Direct reaction blood was determined by the amount of ethylene supplied and pre-calculation. /- Determined by the combination of Hegisen and blood joints 81. This allows the yield of Polymer B to be determined.

Immediately after the completion of the first stage polymerization, purge hydrogen, set the polymerization temperature to constant L1 shown in Table 7, add /-hexene, butane, etc. as necessary, and continue to supply ethylene.
The polymerization reaction is carried out while keeping the total pressure and polymerization temperature constant. Table-7
(H,/xfvn) gas phase molar ratio and (1-hexene/ethylene) liquid phase molar ratio are shown.

The amount of blood reaction is calculated based on the cumulative amount of ethylene supplied and It
It is determined by the total amount of /-hexene copolymerized by calculation.

This allows the yield of polymer A to be determined.

Table 1 shows the results of measuring the physical properties of the obtained polymer.

// Comparative example-3, 9,! Commercially available film 1 node 3 (commercial product A) measured under the same conditions o, og θ9SA Tei gO/7q
(Commercial product B) Ko/Q91b '10
0 233-(Commercial product C) θ7? θ differential 9
0θ, 2.2 Example-6. Rigid Example-6 A reaction was carried out in the same manner as in Example/-j, but in this example, the polymer A was mixed in the first stage, and then the polymer B was mixed.

Therefore, hydrogen was added at the start of the second stage polymerization. The polymerization conditions and results are shown in Table 1.

Example-7 Using /-butene as the α-olefin to be copolymerized,
Bleeding was carried out in the same manner as in Examples 1 to 2, except that the supply of l-butene was stopped using a feeder. The polymerization conditions and results are shown in Table 1.

Comparative Example-7, 7 #O) Crepe f cyclohexane/l and solid catalyst component (A): 10 tsp/? Raise the temperature to θ℃. Next, 6 mmol of triethylaluminum θJ and 1 tsti of hexene were introduced together with ethylene, and the total pressure was
The polymerization was started at 241 kg. Polymerization was carried out while supplying ethylene to keep the total pressure constant, and after 1 hour, ethanol was introduced under pressure to stop polymerization.9.

The polymer was in a dissolved state in cyclohexane, and Melt Intex had 0.0. G j! / / 0m1r+, density is θ, q
In the temperature range of solution polymerization, as in the case of 17a C, it is not possible to obtain the product molecule i1 fixed aggregate B, which is essential to the present invention.

Example-g A polymerization reaction was carried out in the same manner as in Examples/~3-, but in this example, (A) was used as the solid catalyst component, and triethylaluminum was added to 0. Table 1 shows the polymerization conditions and results using Jummci1.

Claims (2)

[Claims] (1) When copolymerizing ethylene with other α-olefins in a hydrocarbon solvent under slurry polymerization conditions using a catalyst system consisting of a transition metal compound component and an organoaluminum compound, A solid catalyst component containing a magnesium compound and a titanium compound is used as a component, and (a) the reaction mixture obtained by polymerizing the chassis reaction in one stage, that is, in a reaction zone of force 1, is further polymerized in a second reaction zone. and (b) in one of the first and second reaction zones, the molar ratio to ethylene in the gas phase is 0.0.
0 / -0,! ; in the presence of hydrogen, the molar ratio to ethylene in the liquid phase is 0.1! r~/, number of carbon atoms in 2~l
Co-polymerization of ethylene and α-olefin coexists to produce a copolymer with a viscosity average molecular weight of 150,000 to 70,000, dense tWO, and θθ to 0.9. A is produced from 3olt1% to qoz% of the total polymer production amount, and in the other zone, the molar ratio to ethylene in the gas phase is θ, S to ethylene in the liquid phase in the presence of hydrogen on the left. The number of carbon atoms in molar ratio is l~3o, y~/co α-olefin, Jt = copolymerization of ethylene and α-olefin, viscosity average molecule M10,000~S force, density f 0 , 90 !
Copolymer B of -0.9o-i/cm is produced at 7θ to 30 it% of the total polymer production amount, and further (viscosity average molecule i of polymer A)/(viscosity average molecule lid of m copolymer B) s-,
t and t, and (c) the melt index of the finally produced polymer is θ-0/~0. ri g / / o > y, dense tx o
, q 10 to o, q 4t o i//crt+. (2) The transition metal compound component has the general formula %% () [wherein, XI and xl represent a rogen atom, and R
1 represents an alkyl group, an aryl group or a cycloalkyl group, and D represents an electron donor compound selected from ethers, carboxylic acid esters, alcohols and amines. 1 is 0. / represents a number in the range of 10θ. m is a number in the range of 1 to q, n is θ~/
represents a number in the range such that m+n corresponds to the titanium valence. p is a number ranging from - to -00. ]
A solid complex represented by the general formula % (1 [wherein, R2 represents an alkyl group, an aryl group, or a cycloalkyl group, and x3 represents a rogen atom], and q represents a 7 to 7
Indicates a number in the range of 3. The method according to item 1, characterized in that the hydrocarbon-insoluble solid is separated from a reaction mixture obtained by reacting the organoaluminum compound represented by: