JPS59145205A - Polymerization catalyst multi-step manufacture - 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] Inventively rounded with a relatively narrow diameter distribution and 9 #1ffi7
J: relates to a method for producing Ziegler-type shielding medium particles having a diameter of about 10 microns or more, preferably 20 microns or more. The novel catalyst is useful for polymerizing a-olefins to produce polyolefin powders.

The stereospecific corrosion of α-olefins in pyrene is well known in the industry. Polypropy V) Jou B* became a glass tick that captured Sesho's city-@. The sales value of polypropylene powder is also increasing rapidly at present, and the amount of polypropylene pellet OM filling is also increasing rapidly. The popularity of polyglopylene powder is at least in part due to the rapidly increasing use of filler, filled polypropylene grades, kerosene, or talc-filled grades.

Most consumers agree that polypropylene powder has all of the superior qualities available in a uniform pellet product, along with good flowability, a low profile and a It also has the quality of not having large aggregations of particles (large aggregations of particles). It has been discovered that a polymer ayg consisting of broken particles has these desirable physical properties.
), the particles themselves also have a relatively narrow diameter distribution and a roundness t'J? It was discovered that it had to be elaborate and elaborate. +1 to wake up one more big powder board meeting! I! The particle diameter of the medium must be at least 10 microns, preferably at least 20 microns, most preferably at least 35 microns, and conventionally it has not been possible to satisfy all of these objectives simultaneously. ◎A fluid medium of dense particles with a narrow particle size range and roundness? eH can be produced, but the average particle size of the product is very small. Although it is possible to construct a thick fx8 catalyst TIA, it is necessary to
By passing the grain through a sieve to separate relatively large particles from relatively small particles, the average grain diameter can be increased, but there is no use for the discarded grain powder. Therefore, this method can be used as a tool for producing large particles according to your wishes, which has been abandoned due to uninventive force in the 1990s. - Another small but desirable surface preparation method for particles with bamboo characteristics is British IV! It is disclosed in the specification of Japanese Patent Application No. 1.139,45θ. In this case, a single step process is used in which T 1014' is mixed and reduced at a low temperature. Ti11. and a reducing agent (e.g. dietheraluminum chloride rDHACJJ) are mixed at the mouth width (140 υ to 115 υ) and heated at 25°C to 45' while stirring.
Heat steadily until the ripening of O 1) I! 3Ao y
When using z, the temperature must be below -5υ.

Maintain reagents at least 2# degree of maturity.

It has been discovered that ethylaluminum dichloride (EhDO) can be used as a reducing agent to obtain relatively large spores. Even though it's so cool, its construction is
Proportional power of the produced catalytic compound Al0I3! Relatively high, l)
I! The activity is 1 compared to the catalyst I left in iAO.
The choice of reducing agent therefore depends on the requirements of the application.

Of course, a mixture of ngaa and EIXJ can also be used, as can triethylaluminum (tTgA).

Inventively, the particle size is relatively large (e.g., the mean diameter of the particle is 10 to 20 microns, preferably 20 to 200 microns, most preferably 35 to 50 microns), and the particle diameter is relatively narrow. Provided is a method for producing a Ziegler type catalyst consisting of rounded and dense particles.

According to the present invention, during the reaction of Ti1l (reaction with preferred diethyl aluminum chloride), a dispersion of a finely divided ready-made catalyst in I/ci11 is prepared as a homophase.
! 2 to produce the final product. In this way, it is possible to generate the #I collection of catalyst fine powder in the same manner as the growth of aggregates to obtain the desired product. The 200 micron enclosure is also round #! A dense olefin-like antipyopathic medium Ti1l enMUlm (ft, nu about 0.
15 to 0.50 or approximately o, a to 1.0 neu) kfi,i! I provide 0 methods for each step below.

a) Jilla is a nine-solid catalyst that has almost the same chemical composition as the catalyst product described in M.
c! Generation: ``It is divided into a thinner part than the snout, and Tt U
14 and H, Mg, I (MgX, NakL, Ml
A reducing agent selected from m or Rx MXm -x (tomodashi, 几 is a υ□~C5 alkyl group or an alkyl group,
Mg1rJ magnesium, Xa (JJ, Br or ii, M
ldAl or Periodic Table aIA%lA% nB or *IA
The metal of N, the valence of mrtM, and X are bluer than the valence of M or an integer smaller than that. ) mixture with 2.
Both Ti014 and the primary reducing agent are Shima, but N
Unreasonable inactivity selection I TE J A [9, ii 5 At a sufficiently low degree that the reduction rate of Ti014 is visible, the gradient formed.

n) Heat at a controlled low speed of 0.2 υ/min to 2-0°C/min until reaching +25°C while heating the 4-pixel mixture ◇ on the Ziegler type catalyst from T t U 14, There are several types, each of which produces a reduced Ti (313·nAlols mortar).

It is preferable to use a reducing agent to prepare the 9yR immediately after using the reducing agent. When diethyl aluminum chloride (DgAU > ?f-) is used as a reducing agent, n is 0.15 to 0.50, and theoretically nσ0
．． 5 and p is usually 0.28 to 0.43.

When ethylaluminum dichloride (EADU) 11' is used, the value of n is 0.3 to 1.0. Normal AI (J
, the higher the 13-functional content, the higher the catalyst activity (expressed in grams of polymer product relative to grams of catalyst used)
The level decreases. If f is applied to the shoulder of the reducing agent 7 times, the Al0I3 content will decrease and the ratio tfji medium will be expected, but the particle size a will become smaller.

To put it more precisely, the solid catalyst has a “grasp” for forming Shao crystals.
Not ■Because in the present invention, α as “I”
Even if you use one piece, the product aβ one piece kII! ! Just as in the case of using a- and β-TiO13i mixtures, data KJ:l) have been shown to be obtained by Totsuta et al. If true Shao crystals are included, the resulting crystal will have the same form as the seed.For example, if it is α-complementary, an α-product will be generated. Furthermore, the effective fireflies Lυa in a convenient σ crystal seeder must be much larger. To simplify the nomenclature, the solid catalyst r and below will be referred to as heat and heat dissipation media.

1. As the unfavorable medium, a catalyst [powder modification] with a wide particle size distribution or a narrow particle size distribution is used. [4*J touch I$, in the second stage 1 (method 9) silk can be produced appropriately in each stage. Can the same reactor be used for both stages in this two stage method? , to the punishment from which the first stage of oppression begins, the total T t 0
14 will definitely be reduced when you hold 1 (hold
ing time) Y:, photon using ◇reduction/reduction several times until the desired average particle size is achieved.
Step t - The reduction in the presence of a 6d catalyst which can be repeated is preferably carried out 3 to 9 times. Generally, the 451 catalyst used in the reduction/crystallization step is used for the production of the catalyst. Same reaction conditions as? use. These conditions are described below.

The side catalyst has almost the same structural formula as the final product and may have a wide or narrow particle size range.

Show examples of horizontal catalysts! Shown below.

table! Example formula of horizontal catalyst: Tmu013・0゜37AIO1,5 Catalyst type: β Average diameter = 18μ Diameter distribution: 15-21μ 41f, 1N medium use mriJ species fIs Reduction/crystallization installation for medium coating 4η 0 based on all of the melting medium that is prayed for (in a multi-step operation,
Even if the amount is increased by the previous seeded reduction/crystallization step, this is compared to the next solid medium.
It is considered to be a l-5 vehicle. ) Even more/Jjic is giving back/
100 Jlfi part of the total catalyst obtained from the crystallization step (i.e., the tow particles, the pollutant produced by the crystallization process).
1 to 75 parts by weight, preferably 20 to 40 parts by weight. That is, 90.33 to 99 per 1ai part of the horizontal catalyst
Filler part, preferably 15 to 4. (A new medium in the pupil is generated.

As mentioned above, regardless of the reaction conditions, whether or not the present invention generally produces the 91'4 compound (i.e., it is produced as a first step), It is the same regardless of whether or not a borage medium is generated.

The reaction conditions are selected to promote crystal growth without excessively producing new fxti crystal nuclei. By mixing the reagents at a low temperature where no slight reduction occurs, the amount and rate of reduction can be reduced to 1F - heating rate of the reagents. Thus, 1 and 1 are important variables for the present invention.

Mixture rr -40°C to +15°C, preferably σ -5°C to -
It is produced in a temperature range of 30°C.

When using gADo'r as a filtering agent, mixing temperatures as high as 25° C. can be used. If this warmth is limited, 1
This is because above 5'0 (25°C and above in the case of F3hDO), the #bottom of new nuclei begins to be seen, and an excessive amount of catalyst fines is generated due to these small nuclei.-40
Since the reaction rate is negligible at 15°C, there is no need for a -40"Q temperature drop. Therefore, the reaction mixture is
0.2 to 2.0 υ/min, preferably about 0.5″07 to a holding deviation of ~40°C (preferably about 300°C)
Heat for 4 minutes. In order to complete the reaction, the mixture is kept in this state for ~2 hours (preferably about 30 minutes).
◎This activation can also be carried out without stirring, as described in detail below. O pressure σ is not critical. . Through line, 10-140 psig
(0.7 to 9.83 fJ), preferably 1 & 4 of σ14 ps g(0.98-). It is only important to use sufficient pressure to keep the irrigant in the liquid phase. For substances, it is carried out by suspending the molasses in an inert reaction diluent that does not serve as a solvent. Straight-chain or a-branched paraffinic hydrocarbons having 5 to 12 carbon atoms, such as heptane and isooctane,
A typical #i diluent to be used is one that does not substantially contain aromatic hydrocarbons. filK unreasonably 4
Table 0 showing the test results for the appropriate isooctane diluent ■ Isooctane diluent 2.2.4-) Dimethyl penta: / 78,
8vo10%2.3-dimethyl pentane
7.92.4-dimethyl pentane 6
．． 22.5-dimethyl hexane 1.5
2-Methyl hexane 1.43-Methyl hexane 1.12.4-Dimethyl hexane 1.1 Isoparaffinic compound in the pond 2.0Till and reducing agent rt〇Reactant used as quenching solution of diluent boiled too much When the amount of decreases once, the catalyst particle size increases, but
At the same time, it was found that the density of catalyst particles decreased. g
Although it can be mixed with ADo 'j Dfi3AO for one-time use, below is a reducing agent (L as an example) BAU'
! Use e. 5hDo*If used, D Hitota 3-4
Preferably, a mixture of 1 part [R and 1 part gADo] is used.

1) It is preferable to prepare a 14AU swamp solution first and suspend a solubility medium in the instep. 0.1 for DBAOB degree of mortar armor
-7 mol, preferably in the range of 5-t,o mol, and 0.5-4 mol A degree, preferably 1.5-2.0 mol A degree. Sowing liquid 1) M (J
0Titll is added to a one-part suspended medium solution over a mixing time of 10 seconds to 4 hours, preferably about 30 minutes, while maintaining the reaction zone at a low temperature. Preferably, a seed catalyst is present when the reaction is carried out.

When reducing σ, Ti1l, to get the profit of non-invention t4, the presence of Kd medium is force 11, Ti1l falls, and DkOm yiJEo j!
Il for krs %ugAU number! The molar ratio of 1 (Jl) is 2.0 to 0.
5, preferably about 1.3.

O shown in Table IK in Working Variable a Table 1 Working Variable Minimum Maximum Optimal Reduction Stage I Direct-11 Medium Average Particle Diameter (μ) 3 40 1
8 Total powder product Zoo parts 9 weight 1 75
20-40 reactants Ti0l and diethyl chloride 0.5 2
．． 0 1.3 Molar ratio of Al minicum Mixing 1 grade under reaction conditions ("O) -40+15
-5 to -30 mixed +lJj tg
Shoma 4 episodes 30 minutes sin heat speed (υ/min)
0.2 2.0 θ, 5 protection! dlf('O)
+25 +45 +401 dumbfounded N
Existence (…(+!#listening) 0
2 1/2 iE power tpsig) 10 140
14 Mixed energy (Watt/A') 100 3
00 200rl; *J step 4 Mouth fever J! IA degree (0! minutes) Non-worldly warmth (-0) 145 185
1601MF: j hours) 30
120 60 Mixing Unnecessary catalyst product '1' i U 1311n/L l(J 13, no. n(rl average particle diameter (μ) 20
20'0 24-474 mixture In order to disperse the di-medium well and to promote the production of relatively thick round 111" 3-sized catalyst particles, reduction/crystallization reaction was carried out. One thing you need to do in t-reaction 4A is Bi 1 Jikunin 1.139,450 Shunmen 1
A good guideline for mowing the mixed conditions that should be used for RA4 is provided. If the mixing energy is too small or too large, catalyst fines will be generated, so the mixing energy ff1tz must be determined depending on the reactor used. energy! ! k (expressed in watts/l), reactor structure, blade shape, baffle plate arrangement and ff! Depends on the viscosity of the I liquid. The optimal hidden value can be determined experimentally (in general, 1
V/l from 00 to 300 is excessive.

In general, flat blade turbine impellers are used.

1 or more 1. /, lJ In a container with M ratio rll
The number of required one root wheel Oe is almost equal to the LAN ratio. For example, if the reactor's LAN) ratio is 7511.9, two impellers are placed at a distance of 1 to mix the whole reactor 'Ir: The design is shown below.

Bi 3rd section is approximately 18 inches (approximately 46 cm, 'm), Q ratio is approximately' 1.0 +7)
ler) In a reactor, six blade turbine blades were packed 10 inches (approximately 25α) from the bottom of the single blade. Each vane is flat-seated and installed with an approximately 45" internal length.

The diameter a of the blade*cradle was approximately 14 inches (approximately 360 mm). Complete z of 2 plates attached at 180'414t;
Good results were obtained when operating at 100-150 rpm using an engine. The mixing energy input σ under these conditions is approximately 100 to 5ooW/4, and the baffle plate is 1 inch (VC1 inch) from the wall of the container.
, 5, 4 CIlI) Ill spaced approximately 2 in the radial direction of the container.
inch (5.08 m) and extended vertically the entire length of the reactor.

Mixing must continue during the mixing, heating and holding stages.1. Of course, the process of activation can continue.

In the presence of a seed catalyst, one or more (preferably 3 to 9) continuous reduction/shao crystallization stages are used. In accordance with the instructions given to British Hour Hand No. 1.139,450 Ming J 舊 in the first 16 medium, and 1! [! It can be prepared as described in the article (the addition of stock and seed medium is omitted).

Thus, the mixing, heating and holding steps can be performed to produce a first heart medium product 11- with or without a narrow particle size range 1741. It must be used to complete the start-up phase. Co-motorization product a
It is preferable to separate the reactant from the reaction solution by, for example, decanterizing it from the reaction solution dipleg K into the reactant for the crystallization step. Pre-generated (r, rfflJ), fl
When carrying out two or more reduction/crystallization stages PiI in the presence of a medium, it is preferable to decant the liquid tube each time Ti114 and D Soda are removed. Also,
Reaction dk You can also leave it there and die.

In which case VC's? Even if the reactor is 73. 'er
'i 6ff mixed yga (-to ~ +15℃) & 1m
L, Tl01. and DEAO7 above side and L
Diluent can be added as desired (ie, if any diluent remains in the reactor, the moles of influent must be suitably high at a time). T 1 (J 14) of the newly added reactant flow armor
is first added to fiTi (molar equivalent of J14, 90.2 ~
The amount is 4.0 mol (preferably about 1 mol).

The reaction mixture is then heated at a controlled rate of 2-2.0°C/min to a final temperature of about 25-45υ, preferably rl.
o, heat at a rate of 5 υ/min to a holding temperature of 40°C.

If the retention shrinkage is not at least 40°C during the retention time, FflI! s Imitation powder can be seen.

In order to prevent this, ffkmaKw of σ, 40υ must be used.0 If this small amount of reconnaissance powder is acceptable, a ratio of σ, 25 to 40°C, and an extremely low range can be used. The retention period t4 T 1L) 14 can be as long as 2 hours to ensure complete reduction. Preferably, the holding interval is at least 30 minutes at 40°C. Stirring 1! Maintain the same speed as during the mixing stage and the 770" fI!% stage for one hour of the holding time. The product produced by the process of the invention is a substantially spherical, compact L medium of large particle size, with a narrow quadratic dynamical saturation of one size. .The final average mosquito particle diameter (and σ if the dry discharge of the particle size of the two-hammer catalyst is wide)
, size distribution) is determined by the number of times the botanium is repeated through the reduction/refining office.

The enlarged photo taken by JKK shows that the agglomeration of the powder is occurring in an uninvented manner. Thus, the present invention has two
This is interesting because it gives the h5c length of a powerful medium with a simple pH of 6. These images also show that rounded and spherical particles are produced in their agglomeration, and that polymer powder particles of almost the same shape are produced.To explain the non-invention The following example is shown below.

In each case, the formation of the medium was carried out by reduction and crystallization in the apparatus described below and according to the method described below. A 500 m1 round bottom flask equipped with a flat-blade stirrer, a flymeter and another inlet was placed in a dry ice/in-octane bath.
@Reject. The stirrer has an angle of 180° [with two blades attached and has a total diameter of σ6cIn]. The entire apparatus and all soybeans are kept in an inert gas. Add diethyl aluminum chloride or other reducing agent (n-hebutane [1.0 to 1.5 molar concentration) to the cooled flask. O diethyl aluminum chloride solution r210 to 400 r
1 of pm! The mouth stirring speed for stirring once per degree is maintained as close to 9 as possible to the certified value, that is, 25G±1Orpm. Diethyl aluminum chloride T
i U 14 (1,'5-2.0 molar concentration, li-heptane A) added at a rate of C3 mmol/min 0 total'rt
at4+am addition ratio (14L33 mol of TIC per 1 mol of aluminum chloride), mixture 11
Heat at +46'01/m at a rate of 0.5-07 minutes. The reaction mixture is maintained at this mg K K& for 1 hour with stirring. At this 0 point, the reaction mixture can be heated directly to 1°C or cooled to 0°C until the time of high activation.

After aging at 40°C, filter for 6 yts and wash 2 times with heptane.
(using 5% diethyl aluminum chloride suspension), the catalyst was resuspended in glass-14M hebutane with 41°C of magnetic stirring. The amount of heptane used for condition ψ and reconsideration 44 is usually three times the volume of the medium.

Seal the container containing the reaction mixture at t1 + 1 JI K
Heat at 0160υ for 1 hour (160°C K) for 1 hour (... After aging, cool the crystallized material for 2 to 4 hours ◇ This 7J11 thermal browsing medium may or may not be stirred.di I've washed it twice with heptane,
In the description of the invention, the reduction/shaoxing is separated from the resulting catalyst-deficient reaction mixture and heated for activation. It is also possible to repeat the process three times (Examples 5 and 6). During the entire crystallization and reduction reaction, including both steps, the reaction mixture was charged with two blades of 6C1Ft (on an impeller of diameter D, c
9 Stir. Torque force i10 to 25 inches (
72ONl 80011-Cura) range t can be taken.

Example I 41 of 2.274 mmol/flLl in H-heptane
A solution of titanium 31ide in n-hebutane was similarly prepared.
stost remol/ml diethyl aluminum chloride m Rk M 'A L fe@T 4014 di
77 cc (170,55 mmol) of liquid and 79.42 cc (127,91 mmol) of diethyl aluminum chloride
A mixture of 1 t-aoυ (mmol) was prepared in 1 t-aoυ. Ti(3) for diethyl aluminum chloride in this mixture
The molar ratio of 14 is about 1.33, and it is finely divided into 113.1/2A10130.7011'l (
However, it was 2 times the total catalyst finally produced.
When diethylized aluminum swamp Q K 0.8 cc was added to the mixture t6 T i 014 f4 fft' at a rate of 0.8 cc 7 minutes, the proportion of the mixture t6 T i 014 f4 fft' was approximately 11%. 〃During the reaction of a:... and the remaining 9, the stirring speed was approximately 25%.
I supported OrpmK. The temperature was increased at a rate of about 0.5'Q/min to a final degree of 4 at about 40°C, and at 174°C/7
rI heat r end. Filter the powerful medium, wash with n-heptane, +'! in heptane! +lζ field @E medium r investigation t
It was found that Mi rice has a particle size distribution of about 13 to 31 μm. The particle distribution was wide, irregularly shaped, and black in color. This meant that if the uninvented VC & Since a melting medium is used, it is shown that σ is insufficient. Hebutane antiseptic solution was used.

TIU14 m H75CO (170.6 mmol) Tojetil aluminum chloride relative 79.4 cc (127,
9 mmol) and Oita Don-heptane 79.4 ccO
Seikyo [Titanium tetrachloride bath number t1.6Cc/min #JR4 speed was added to the wet solution of diethyl aluminum aluminum at a temperature of -30℃, and the stirring speed was 30℃.
0rpn Ic.

The reduction reaction was carried out in the same manner as Hg7tJi. ◎The temperature was raised to 140°C and heated for 30 minutes to form a product.
! After t, % mti, * was cooled again to -30°C and a layer of titanium tetrachloride, 70.9 g, 1 diethyl salt and 79.4 cck of aluminum were added. The meeting again 0.5υ/
Raise to a final temperature of +40°C at a rate of 11r@
It was darkly matured.

The catalyst product obtained from this reduction reaction had a spherical black color with an average diameter of 28 μm and a narrow particle size distribution. Ilcσ did not appear to be quite dense and abundant in the catalyst structure, as with other products of the invention, but there were no structural "wiggles" in the structure.

This product #3 was then activated as previously described in the book 100, and was used in the synthesis of propylene tIA, but with n-hebutane A as a reaction diluent.
It was found to be an excellent catalyst for the polymerization of polypropylene, with 27 g of polypropylene k (17 t) per gram of solvent. The product r!
Boiling n-hebutane had a stale substance [1596 Doshin's words] indicating a high degree of crystallinity. The intrinsic viscosity is 2.
It was 74.

Example 3 To illustrate the use of preformed catalysts, we used an irregularly shaped melting catalyst with a small particle size and a wide diameter radius to illustrate the reduction/crystallization phase. The method of using it as a feedstock in ffjK will be described. In an exceptional case, a preformed titanium trinomide catalyst of the formula 'l''f013.0,33Δ1 (J13) 4.16 IIt 86.05 mmol of the diethyl-acclimated aluminum solution described in Example IK (
53.5 cc) Added 54 cc of additional n-hebutane to the instep to make it cloudy. This mixture Kfllll&C g titanium tetrachloride [g50 cc (113 mmol) tO,8
@Mixed #lJ added at a rate of cc/min was initially 240
While stirring at a speed of rpm - 7 to 30°C.
To next I/C mixture kO ladle at 40°C at 05°C/min.
and then aged at 40'O for about 1 hour.

The original catalyst had a wide range of particle sizes and a large amount of catalyst fines; however, in this experiment, the product a had an average particle size of about 16μ, with a narrow particle size distribution and an irregular shape. It was huge and black. The structure was dense and the shape of the 90 catalyst particles was irregular, but this is because the original catalyst was not irregular, but by repeating this step, a regularly shaped product with a large average diameter was obtained. It is expected that a temperature of +5C or lower, preferably -15 during mixing the yuzu substance and catalyst, is expected to be obtained.
Maintain below υ. It was also discovered that although diethylaluminum chloride is the optimal reducing agent, large particle sizes can be obtained by adding a small amount of ethylaluminum dichloride. Therefore, ethylaluminum dichloride accounts for not more than 25% of the reducing agent and other Although diethyl aluminum chloride is preferred, it is also possible for the reducing agent to contain 0-100% diethyl aluminum chloride'.

In other cases, the preferred reducing agent can be mixed with triethylaluminum in an amount such that the ratio of the reducing agent to diethylaluminum is between 0 and 0.25.

Example 4 In an unusual case, the vehicle [Q is prepared first, regenerated separately,
It is then treated in the straw two-stage order of the invention described above.

9111 N-heptane #j of tetranomized titanium described in K
[25 cc (2,27 mol) kl of catalyst prepared and separated as above at a rate of 61 cc/min.
it 4! 160 cc of diethyl aluminum chloride solution (0.8 molar in Hegetane) were added to the solution.

The entire reaction mixture was stirred at -300 at a rate of 250 rprn while adding 314 gj solution. After the addition, the reaction mixture was heated to +40"O
Heat at a controlled rate of 0.5υ/min until K is reached @
After the amount of t'tI'g medium reached a theoretical yield of 98%, the mixture was stirred for 1 hour at t+40υ. j”E
Narrow as i medium grain diameter/I5.

Example 5 In 9IJ, 2sigma and 19catalysts were added to multiple 5hot technology as described below.
Manufactured by kAta. The TIUl of S degree given in Example 1, 7tnti of n-hepta, and H-heptane liquor of Alnt 201 were similarly used in this example. a1gt2(
A mixture of 79.4 cc (127.9 mmol) of Jl Numaba and an additional 79.4 cc of n-hebutane was prepared (resulting in a concentration of about 0.8 mmol/ml in Atgt, ox:t!!) OAIEt20f @gllc]
75 ccOTio14 (170.6 mmIJ% LeFar) was added at a rate of 1.68 C/min at a temperature of 20 °C. The molar ratio of Ti(JI/diethyl aluminum chloride) was approximately 1.33. Stirring Reduction reaction a was carried out in the same manner as Example 1, and the rate was increased to +40υ1.
After aging the product for 30 minutes, the bath was cooled again to -30°C.

This catalyst product is the preformed catalyst for use in the Kf of the present invention. Add concentration AIEt201 bath fi1 to the reaction mixture
7.9 cc (7.155 mol'mK in n-heptane)
Then, the reaction mixture was stirred at -3oC for 20 minutes at 9υ, 37°6 cctDftJ degrees T.
I (Jl.

(4,55 molar concentration in n-heptane 1 &) t-add t.

O! The A1 degree was increased again at a rate of 0.5°C/min to +40"0O maximum iP, tm degree and aged for 30 minutes.
The molar ratio of 0I,/diethyl salt 11S aluminum is approximately 0.
．． 75 and t. +fil stage 72 times or more. The catalytic product from the last reduction reaction is black, spherical, and has an average diameter of 24μ. Changes in anal mosquito particle diameter due to the quadruple reaction are shown in Table ff below.

Example 6 75 CC(DTIUI 4(ri n-hebutane liquor?I
L 2.274 moles)? cAiI and 1
35cc A1gt012 Hebuta y#i (t, 89moni/!Ikt) Y, na. C mixture 1yσ-20℃
The experiment was carried out in the same manner as zero reduction lamp test 1, in which the stirring speed was σ240 rpm in a reactor with a baffle plate. Reduction reaction 6 was carried out in the same manner as in Example 1, and crystalline product 1 was obtained by aging at 140" CJK temperature (heated and aged for 30 minutes), then the solution was cooled again to -20°C, and 135 cc was added to the solution. Al of
flt01'2 solution (1.89 molar degrees in n-hebutane) was added. Then, TjL of 37.6CC) l of I4
f-hegetan aff (4,55 mol) f Z Q minute fl-o vortex e'? r: 0.51' again)
The final vorticity was increased to +40°C at a rate of 7 minutes and aged for 1 hour at this degree.

The reaction of Kukouji described just before was repeated two or more times. The admixture produced from the fourth reduction reaction had a flat diameter of 47μ, and was narrow and black spherical in shape. The A91 medium structure rX was dense. The resulting changes in catalyst diameter Vcsp and τ for each successive reduction are shown in the table below and explained.

From Table 3, it is clear that comparatively large catalyst particles can be obtained using the present invention, and even when the pre-formed catalyst has a wide particle size distribution, the particle size distribution becomes narrow.

Al lightning 2t)l, AIFltO12 and AIEt3
Furthermore, a mixture of Nire et al.@σ is a preferred organometallic reducing agent, and suitable organometallic reducing agents include R2Mg, RMgX,
Nal, MR, m 51u RxMXm-x (friend, Rrj O1 - the above alkyl group or substituted alkyl group, Mgd magnesium, X1U1, Br, also dI, MI
riALX of the J periodic table, [lA%IA, IB or *I
Gold of group A, m 91 The valence of M is a swordsmith equal to the valence of xtast, or an integer smaller than that. )
There is.

Furthermore, as listed in the preferred activation time and time σ table, a wide range of activity 1t is possible [690-185° C. for times between 20 minutes and 5#].

Further, while average particle diameters in the 'a range of 20-200 microns are standard, there are rare cases where average particle diameters as small as 10-30 microns may be used for exceptional Vci applications.

The burr occurs during the first stage reduction of Tl0I with AtBT3, which is an unusual example of the formation of extremely small catalyst particles, particles with an average diameter of about 3μ. However, the positive media of these relatively small particles are extremely active. Also, those uninvented techniques! can be enlarged to a satisfactory size.

Thus, the first stage reduction VC process using AIBT2tJIK of TiU14 produces catalyst particles having an average particle size in the range of about 3μ.

These 3μ-sized particles, Xfi1, can be processed through a series of rings/robustization stages, e.g., multi-stage operations, to obtain an average particle diameter/diameter that is at least 1 to 10μ in size. It can be done.

Uninvented refreshing square-like homophone 1: Also described below.

fl) The four-element agent is selected from diethylaluminum chloride, ethylaluminum dichloride, triethylaluminum, and mixtures thereof. ) The average particle diameter range is 20 to 200μ.
It is assumed to be 4 signs. The method according to claim 1, characterized in that the sum of + (4) PI generated as 6 pre-generated 9 particles between the reduction dash lines in the previous stage of reduction stage 14r1!脣FI characterized by performing at least twice consecutively using a medium
The method described in the first item of the fsl calculation range and the above items (1) to (3).

(5) − or more stages 4IC1? The reaction conditions for
Claim 1 and Upper 1ietl)
to (4) the method described in fJ4.

(6) Repeat step I4A s Hk at least twice,
After that last repetition, 1! It media product total 90-185"00 temperature, 20 minutes-5 hours 1
The method described in paragraph 1 of the circular claim and the above tit.
When the crystallinity is 145-185℃, the above-mentioned time is 30-1
8) The method according to item (1) to (7) above, characterized in that the reducing agent is diethyl aluminum chloride. 0 (9) The method described in items (1) to (7) above, wherein the reducing agent is ethylaluminum dichloride.

+11 The method according to item +1) to (71) above, characterized in that the pre-txb reducing agent is triethylaluminum.

α0 The method described in (1) above, where the thickening agent is a mixture of diethyl aluminum chloride and ethyl aluminum dichloride, and the method described in JJK is used. The composition is about 4.55 molar degrees, and the goodness of diethyl/I/aluminum chloride is about 7.1.
5 molar concentration, initially diethyl aluminum chloride r
Addition of diluted J to 3 to 5 molar degrees by mixing with the additional diluted solution and then adding TI to the selected diethyl aluminum chloride at a relatively slow addition rate.
1-The method described in Section 2 of Section A of Patent A'14.

1 yam Mixing a: Approximately -20℃, heating rate approximately 0.5υ/
minutes, the holding temperature is about +40°C, the holding time is about 30 minutes, the mixture'is 3 to 9 reductions, 71D heat and holding stage 1! was repeatedly cooled to about -30°C at mK! The above αa, [method described in JK・(14Ti1l, added to the top of the bath liquid for 20 minutes,・
The method described in item 03 above, characterized in that the total mixed energy power is 100 to 3 ooW/J.

Claims (1)

Claims: A method for producing a TicIs, nMc1m olefin polymerization catalyst product, comprising the steps of: (i) a finely divided preform having essentially the same chemical composition as the desired catalyst product; solid catalyst;
The mixture of Ti114 and a reducing agent was added to the 'r'tci4
and the reducing agent are soluble, but the catalyst is insoluble, in a suitable inert diluent, where n is, as is known per se, about 0.15 to 0.50 or about (), 3 ~1.
In, the catalyst product is about lO to 20
The reducing agent is formed as rounded dense particles with an average particle size of 0μ, and the reducing agent is R2Mg%⇠MgX, NaR or RxMXm-X (where ⇠ is a C, -C5 alkyl or substituted alkyl group, Mg is magnesium; f2) a holding temperature of +25 to 45°C; heating said mixture at a controlled low rate of 0.2 to 2.0 °C/min while mixing until reaching the formula: 'I'iCls-nM
Using 1 part by weight of the corresponding preformed catalyst, the preformed catalyst was heated to TiC at about -40 to -50°C.
l4 diluent solution, reducing agent diluent solution and 06~CI
2 with an additional diluent selected from paraffinic hydrocarbons and mixtures thereof, the molar ratio of TiCl4 to reducing agent is between 0.5 and 2.0, and the +[i C14 concentration is o,
i to 7 mol and add enough TiCl4 and reducing agent to form 19 to 39 parts by weight of catalyst product during the reduction of 'L'1C14, and the mixture to substantially complete the reduction reaction. - and hold at said hold temperature for a period of time sufficient from 0 to more than 120 minutes to maintain good mixing throughout the reaction zone, and the final repetition of the reduction step, heating and hold temperature step. After that, the catalyst product is 90-185
A method characterized by activation by heating at ℃ for 30 to 120 minutes.