DE1795109A1 - Continuous process for the production of solid, finely divided polymers from olefinically unsaturated compounds - Google Patents

Description

P-70Ü2-C Union Carbide Corporation

Continuous process for the production of solid, finely divided polymers from olefinically unsaturated compounds

Since Faweett the possibility of polymerizing olefins described there have been many significant improvements in the olefin polymers and the processes for "making them."

A milestone was the introduction of a transition emergency

lysators by Ziegler, who specializes in the production of high molecular weight, solid polymers at low pressures made possible. E3 other low-pressure catalysts with advantages - and at times also disadvantages - compared to the one proposed by Ziegler Catalyst system found.

Finding the low-pressure catalyst systems was directed by the Attention to processes for the polymerization of olefins. The most important procedure for the tent is the Aufuchlümmungu procedure, in which a polymer in an internal solvent constant stirring in the presence of a Niederdruekkatalyuatoru will be produced. The inherent in the containment process, the most decisive disadvantage is then solvents, with certain

BATH ORIGINAL

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- P -

Procedural costs and at the expense of average hopping must be recovered. Some solvents can also remain in the polymer and influence the physical properties Properties of the product. The physical properties The slurry complicates this disadvantage and most slurry reactors run at a high solvent content operated to ensure that a stirrable mass is maintained.

It is therefore clear that a solvent-free, low-pressure reaction system would have advantages over the slurry process.

It has now been found that feate, finely divided olefin polymer ^ with lower, non-corrosive catalyst residue can be obtained by continuously passing a gaseous stream containing a polymerizable olefin with a powdery silyl chromate or poly (hydrocarbyl aluminum oxide) complex polymerization catalyst for the olefin in contact in a polymerization zone consisting of a vortex-shaped bed of formed and forming polymer parts at a mass gas flow velocity sufficient to maintain complete turbulence, from the PolymeriBationazone a small proportion of the swirled Bed as a diacrete polymer particles in suspension with part of the gaseous stream withdraws and then the diakretan polymoriaate particles from the gaseous

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Swirling means abiasnnt. The portion of the gaseous stream that does not enter the polymerization reaction is eliminated removed from the reaction zone, cooled to remove the heat of reaction and returned below the base of the fluidized bed, to maintain complete fluidization of the bed and to keep the bed at a temperature below that To keep the sintering temperature of the polymer particles. To keep up practically uniform conditions ("steady πtäte operation") are additional feed gas and powdery catalyst is introduced into the fluidized bed at such speeds as the rate of product formation and the catalyst consumption a are the same. Of the additional catalyst is introduced into the fluidized bed above the base of the bed for rapid catalyst distribution reachable throughout the bed.

In addition to its non-corrosive nature, the catalyst residue is in the polymer particles produced according to the invention low enough to allow the polymer particles to be used immediately without treatment for catalyst removal to allow.

Another embodiment of the present invention directs “I refer to the use of hydrogen to control the melt index and melt flow properties in one Pplymerisate produced by the fluidized bed reactor.

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The present invention is illustrated by the accompanying drawing and the explanation thereof further illustrates the schematic Working of a fluidized bed reactor used according to the invention represents.

According to the invention it is possible to use olefins with 2 to about. 8th, preferably 2-4 carbon atoms. to polymerize. the Olefins only have to be gaseous at a temperature below polymerize the sintering temperature of the polymer obtained and practically dry, finely divided, from low molecular waxes and fats form practically free resin particles.

Olefins can be homo- or mixed-polymerized. Copolymers include the formation of polymers from two or more monomers, such as random copolymers, as well as the

compound

Manufacture of special / polymers. For example, different Monomers are introduced sequentially into a single fluidized bed to form Blookmisohpolymeriaaten. One can also transfer a resin from a reactor containing a monomer through a suitable valve into one reactor Transferring monomer containing reactor, with only an insignificant amount of monomer from one reactor to the other to be led. This latter process can also be effectively used to form polymer blends. Both Alternatives are particularly useful in the formation of block polymers and polymer mixtures of monomers with different reactivities.

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The polymerisation can in the presence of hydrogen for the effective regulation of the melting indox of the polymer and for the improved reactivity of the monomers with low reactivity in the production of copolymers carried out will.

The catalysts used according to the invention are those in Silyl chromate catalysts described in U.S. Patents 3,324,101 and 3,324,095 and the poly (hydroxycarbylaluminum oxide) catalyst complexes described in U.S. Patents 3,231,550 and 3,242,089, which are hereby included in the present application.

The silyl chromate catalysts are characterized by the presence of a Group of Formal

- 0

R. - 0 0 I. It Si - Cr I.

characterized in which R represents a hydrocarbyl group with 1-14 carbon atoms afcoht. Preferred silyl chromate catalysts are the bis-triarylsilyl chromates and in particular

Bis-triphenylsilylchromate. The poly (hydrocarbyl aluminum oxide) component The catalyst complex3 consists essentially of units of the general formula

R.
Al-O-

in which R stands for an alkylate with about 1-12 carbon atoms or an arylate. The preferred poly (hydro

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carbyl aluminum oxide) component iat poly (isobutyl aluminum oxide).

The catalysts used according to the invention are in the form of powdery, free-flowing, solid particles and roll can preferably be further divided. The further division ("subdivision") is the ability of the Katalyaatorteilchen, to break in the presence of the growing polymer and thereby lead to the formation of many polymer particles with a small residue from a single catalyst particle to expand. The catalyst can be applied to a carrier or unsupported, it can be ground or spray-dried Particles are present,

Supported catalysts are prepared by, for example, adding a support to a solution of the catalyst and the catalyst solvent with dry nitrogen to form a supported catalyst evaporates in the form of a dry, free-flowing powder. If the carrier is porous, special attention must be paid to its size be given. When incorporated into a porous support, the catalyst forms active sites on the surface and in the pores of the carrier. Without wishing to be bound to a theory, it is assumed that the polymers on the surface and begin to grow in the pores of the catalyst. Where a polymer that has grown in the pores becomes large enough, it breaks the carrier and thereby sets fresh catalyst parts free in the inner pores of the carrier. The one on one

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applied catalyst can subdivide many times during its life in the bed and thereby the Production of polymers with low catalyst residues improve, thereby eliminating the need to recover the catalyst from the polymer particles. If the wearer is too big, he may break or piss resist; this would prevent subdivision, which would lead to wasted catalyst. Farther a large carrier can act as a heat ally and the formation cause "hot spots". It has been found that carriers with β1π3Γ particle size around 250 microns or less have the ability show effective under the force of a growing polymer to break.

In addition to porous carriers, such as silica, alumina, thore earth, circular earth, etc., other carriers, such as carbon black, can be microcrystalline Cellulose, the non-sulfnated ion exchange resins, etc., be used.

When choosing the catalyst support, attention must also be paid to the possibility of a competitive reactivity of the support with the olefin. For example, silica tends to compete with the catalyst if propylene is to be polymerized as a single monomer and easily causes the formation of low molecular weight propylene waxes. Geiriü use should therefore be veri.ii ed on in the manufacture of polypropylene. But she doesn't seem to understand the catalyst

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partly to influence where copolymers of ethylene and Propylene are produced.

A support also serves to expand the catalyst. They have, for example, catalysts which, by using of a silica carrier have been found to be effective with a ratio of chromium to silica up to 1000.

An unsupported catalyst can e.g. into the bed of polymer particles and evaporating the catalyst solvent. * Both procedures gave dry catalysts capable of subdivision. When spray drying the catalyst must be on the formation of particles of a sufficient size that they remain in the fluidized bed and do not settle under the

standing, continuous gas flow to the head of the bed

the end

because of and dadur_ch / the bed before initiation of polymer formation escape on them. Catalysts deposited on a resin pose fewer problems since they are finely divided Polymerisatteilchen are used in the fluidized bed and act as the original support for the catalyst.

A fluidized bed reaction system used in the present invention is shown in the drawing shown. The reactor consists of a reaction zone 12 and a speed reduction zone 14 °

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The heaktionszone 12 consists of a bed of growing Polymerisatteilchen, the polymer particles formed and a small amount of catalyst caused by the continuous Flow of polymerizable and modifying gaseous components in the form of additional feed and recycle gas be swirled through the reaction zone. To maintain a living fluidized bed, the mass gas flow is through the bed above the minimum flow required for turbulence, preferably between about 2-6 times G ", in particular between about 3-5 × G". G- is in its usual form used as an abbreviation for the minimum mass gas flow required for turbulence (cf.CY. Wen and Y.H. Yu, "Mechanics for Fluidization," Chemical Engineering Progress Symposium Series, Bad. 62, pp. 100-111 (1966)).

It is essential that the bed always contain particles to prevent the formation of localized "hot spots" and to trap and distribute the powdery catalyst of the invention throughout the reaction zone. At the beginning, the reaction zone is usually charged with a basic amount of finely divided polymer particles before the gas flow is introduced. The type of the particles can be identical to or different from the polymer to be formed. If they are different, they are withdrawn with the desired polymer particles formed as the first product. Gradually, a fluidized bed of the desired particles then replaces the initial bed.

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- ίο -

The catalyst concentration in the bed is practically equal to the catalyst concentration in the product, namely on the order of about 0.005-0.50 # of the bed volume, which is of the ' Productivity of the particular catalyst used depends,

The catalyst used in the fluidized bed is stored for use in a container 32 under a nitrogen blanket.

The turbulence is achieved by a high rate of gas recirculation to and through the bed, which is usual is about 50 times the feed rate of the additional gas. The fluidized bed has the appearance of a dense mass of living particles in a flow that is as free from eddies as possible, as is the case when the gas is passed through the Bed is formed. The free flow of the particles and the turbulence is made possible by the fact that the axial pressure drop through the bed is usually on the order of only about 0.07 atmospheres.

The extra gas is in the

Introduced bed which is equal to the rate at which the finely divided polymer product is withdrawn. The composition of the additional gas is determined by a gas analyzer 16 mounted above the bed. This determines the component deficiency in the returned gas, and the composition of the additional gas becomes accordingly adjusted so that a substantially uniform gaseous composition is maintained within the reaction zone remain·

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In order to ensure complete turbulence, the recycle gas and, if necessary, part of the additional Gas returned to the reactor at point 18 below the bed. There is a better swirling of the bed a gas distribution tray 20 above the return point.

The portion of the gas stream which does not react in the bed is the recycle gas which is removed from the polymerization zone is, preferably by passing it into a decelerating zone 14 above the bed where the trapped Particles have the opportunity to fall back into bed. Particle recycling can be carried out by a cyclone device 22, which may be part of the speed reduction zone or outside it can. Optionally, the recycle gas can then be passed through a filter 24 to remove small particles at high gas flow rates.

speeds to avoid dust touching the heat transfer surfaces and compressor blades.

The recycle gas is then passed through a heat exchanger 26 Λ , in which it is freed from the heat of reaction before being returned to the bed. Due to the constant removal of the heat of reaction, there does not seem to be a merciless temperature gradient within the bed. In particular, it has been found that the bed appears to be acting almost immediately to equalize the temperature with the recycle gas to bring it into conformity with the bed temperature, whereby, under steady conditions, it is at a practically constant level

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Temperature. The Rückfüürungagaa is then in a compressor 28 compressed and returned at the bottom 18 to the reactor and the fluidized bed through a distribution tray 20.

The distribution tray 20 is important to the operation of the reactor. The fluidized bed contains growing and formed, fine divided polymer particles and catalyst particles. Since the polymer particles are hot and possibly active, their weaning must be prevented; then a resting mass is allowed to arise, any active catalyst contained therein can be used continue to react and may cause a merger. Hence, the recycle gas is diffusing through the bed at a speed sufficient to maintain the turbulence at the bottom of the bed, The distribution tray 20 serves this purpose; it can consist of a sieve, a slotted plate, a perforated plate, a Plate of the bell-bottom type, etc., Regardless of its construction, it must pass the return gas the particles at the bottom of the bed diffuse to keep them alive; furthermore it also serves as the carrier of a dormant one Bed of resin particles when the reactor is not in operation.

In addition to a polymerizable olefin, hydrogen is a component the gas flow is of crucial importance in the vapor phase polymerization of olefins in the fluidized bed reactor. In vapor phase polymerization, the melt index is des

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Product relatively insensitive to temperature, in that a moderate change in the working temperature does not cause any noticeable change in the melt index. Therefore must if necessary, resort to another means of modifying the melt index. It was found that Hydrogen affects the melt index of the product. Usually the melt index of the product increases with the Hydrogen concentration in the gas flow.

Optionally, also to the system controller either m to the catalyst and the gas Reaktionsteilnehmeminertes be present.

In the production of copolymers from ethylene and propylene or other monomers with low reactivity it was further found that the presence of hydrogen reduces the reactivity of the monomer with low reactivity improved.

It is essential that at a temperature below the sintering

temperature of the polymer to work. To ensure that no sintering occurs, working temperatures well below the sintering temperature are useful. For the preparation of homopolymers, a Arbeitsteraperatur is preferably from about 90-110 ⁰ C., during a working temperature is to copolymers of about 90 ⁰ C * or lower expedient.

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The procedure is carried out at a pressure of about 2.8-21 kg / cm or more, with working at medium and high pressures favoring the heat transfer, since a pressure increase the heat capacity of the gas per unit of volume increases.

The catalyst is introduced into the bed at a point 30 above the distribution tray 20 at a rate equal to its consumption. The introduction takes place preferably at one point about 1/4 to 3/4 of the bed height. The introduction of the catalyst at a point above the Distribution tray is an important feature of the present invention. The silyl chromate catalysts used according to the invention are extremely active. The introduction into the area below the distribution tray could initiate the polymerization cause there and possibly cause clogging of the distribution base. Instead, support it the introduction into a living bed removes the catalyst distribution through the bed and closes the formation of more localized Make high 'catalyst concentrations, which lead to the formation "hot spots" can result.

A portion or all of ^one additional feed stream is used "to guide the catalyst in the bed. Preferably only a portion of the additional feed stream is used as a support for the catalyst since, at high productivities, the introduction of a large amount of gas into the side of the bed can interfere with the properties of the bed and cause "channeling" etc. Alternatively

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1795103

part of the returned Gaastromea can be diverted to to lead the catalyst in the bed.

The productivity of the Bettea is only increased by its agility the introduction of the catalyst. You can by mere Increased speed increase and reduced speed the introduction of the catalyst can be reduced.

As any change in the rate of catalyst introduction If the rate of formation of the heat of reaction changes, the temperature of the recycle gas becomes ..upward or set down to adjust the rate of change in heat generation. This ensures maintenance a bed with a practically constant temperature. A full instrumentation of both the fluidized bed as well as the cooling system for the recirculation gas of course necessary for any temperature change to establish in bed that a suitable adjustment of the temperature of the return gas can be made.

Under a given combination of working conditions, the fluidized bed is kept at a practically constant height, by taking part of the bed as a product at the same rate how the formation rate of the finely divided polymer product subtracts. Because the speed the heat generation is directly related to the product formation, a thermal analysis of the reactor decides leaving gas the rate of formation of the finely divided polymer.

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The finely divided polymer product is preferably continuous withdrawn at a point 34 or in the vicinity of the distribution tray 20 in suspension with part of the gas stream, which is vented before the particles settle in order to avoid further polymerization and sintering, when the particles reach their final collection zone. As mentioned above, the suspending gas can also be used for transfer of the product from one reactor to another reactor «

The finely divided polymer is expedient and preferably made by the successive work of a couple Timed valves 36 and 38 withdrawn which delimit a 4-0 cutting zone. While the valve 38 is closed the valve 36 opens and allows a quantity of gas and product to escape into the zone 40 between it and valve 36, .that then closes. The valve 38 opens and passes the product to an external recovery zone, whereupon it closes until the next episode.

Finally, the fluidized bed reactor is provided with an appropriate venting system in order to ventilate the bed To allow initiation and conclusion of the procedure.

The finely divided catalyst systems of the present invention appear to provide a product having an average particle size of about 20-40 mesh in which catalyst and support residues are unusually low. The catalyst residue is about 0.001 wt. - ^ Chromium in the invention

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Product. The low content of catalyst residue is the attributed to the high productivity of the catalyst and its ability to subdivide. Productivities over 2000 kg Polymer per kg of catalyst were found.

Compared to currently used slurry and Solution methods were used in the work of the invention Fluidized bed reactor noted several advantages.

A major advantage is that the polymer does not tend to coat the reactor walls. The formation of a Polymer coating on the walls of slurry and solution reactors is relatively uncontrollable and unpredictable Phenomenon that hinders heat transfer and "breaking off" of polymer lumps in the system can cause.

The fluidized bed reactor appears to be economically viable cause lower installation and operating costs.

Furthermore, it is more stable because it tends to dampen or regulate any sudden change in working conditions. Therefore, when operating the Wirbelbettreaktora it acheint to give more leeway ·

Finally , the most important advantage is the improved possibility of controlling the gas composition. The gas composition in slurry and solution reactors is limited by the monomer solubility and diffusivity. Since there are no liquids in the fluidized bed reactor, the gas composition is practically infinitely variable and is in the

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Practice only through the relative responsiveness of those present Affected monomers.

The following examples illustrate the preparation of the catalysts according to the invention, the working, as the fluidized bed reactor of the invention and the properties of the polymers according to the invention.

The properties of the polymers prepared in the examples were determined according to the following test procedures:

^ Density - ASTM D-1505. Plates were treated for 1 hour at 12O ⁰ C. to approach equilibrium crystallinity a.

Melt Index - ASTM D-1238. Measured at 190 ^° C. and stated as g per 10 minutes.

Flow Rate - ASTM D-1238. Measured at 10 times the weight used in the melt index test above.

Flow ratio nia =

Melt index

Stiffness - ASTM D-638
Tensile Strength - ASTM D-638
Yield Strength - ASTM D-638
Elongation - ASTM D-638

Tensile Impact Strength - ASTM D-256. The sample was not scored and was clamped in an Izon impact tester so that it would break when stressed.

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Color - This was means of yellowing and whiteness a modified, scaled-down one for reflection measurements Beckman Spectrophotometer, Model B. To recruitment and calibration of the instrument was a "Vitrolite" reflectance standard sample obtained from the National Bureau of Standards used. The reflectance was measured with suitable plates at 430 and 550 millimicrons. The wisdom is that Percentage reflectance value at 550 millimicrons. The yellowness is the percentage reflection at 550 minus the percentage reflection at 430 millimicrons. This test is used for quality control and is similar to the ASTM Test D-1925-63T.

example 1
Manufacture of the catalyst

1000 g of a silica carrier of the following composition i

Weight -jo Dry basis

Al ₂ O ₅ 0

SiO ₂ 97.95

Na ₂ O 0.05

SO. (water soluble) · 0 λ

with the following physical properties:

mesh size; U.S. Standard Wt- $ greater than

60 0.0 max.

100 4.0 max.

HO 10.0 max.

■ 200 '9-33 * ·

Surface area 338 m / g

average Pore diameter 170 Å

that in a nitrogen atmosphere at temperatures of 325-700 ° 0. had been dried, was stirred and under a stick

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substance atmosphere added to 4 1 isopentane in a 5-1 flask, which is provided with a sintered glass filter in its bottom was. Then 41.5 millimoles of bistriphenylsilylchromate were added, and stirring was continued for about 1 hour.

In a second flask, jacketed for cooling and flushed thoroughly with dry nitrogen, 585 millimoles of triethylaluminum were dissolved in 200 ecm of isopentane. With vigorous stirring of the solution and with cooling to maintain the temperature at about 25 ⁰ C., 570 mmol of ethanol were added to form Äthoxydiäthylaluminium then which was then added to the suspension of silica and Bistriphenylsilylchromat in 5-1 flask. After stirring for 30 minutes, the solvent was drained through the sintered glass filter and tested; it was practically free of aluminum and chrome. The residue was warmed slightly and dry nitrogen was passed through until a free-flowing, practically dry, powdered supported catalyst was obtained.

The following examples illustrate the preparation of olefin polymer using a fluidized bed reactor of the powdery, finely divided catalyst prepared in Example 1.

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Example 2 "to 5

A jacketed reactor according to the accompanying drawing with a reaction section with a ratio of diameter to height of about 1: 7.5 and an upper section with a ratio of diameter to height of about 1: 2 at a pressure of about 7 kg / cm and a gas flow rate between 3 and 4 G- operated. At temperatures of 90-110 ⁰ G. homopolymers were prepared, while the production of mixed polymers in 80 ⁰ G. or below was carried out. Hydrogen was used to regulate the melt index.

The polymers produced in this reactor are listed in Table 1.

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Example Table 1 Homopolymers 88 3 I. 95 .Product 2 7th Polyethylene 7th Melt index Polyethylene % 5.0 0.49 19.4 Flow rate 0.05 58.1 - Flow ratio 8.2 95.0 119 80.6 density 162 0.9690 Stiffness; kg / cm ² 0.9670 11 760 O Tensile strength 11 200 42 to
location pjarbe - whiteness 109 - ο yellowness - ^ ropylene content - - CO - average reactor conditions temperature; ⁰ C. ^ jerk; kg / cm £ hydrogen content; VoI-; Propylene content; Vol- $ Ethylene content; Vol- #

Mischp olymerisat e

Ethylene / propylene ethylene / propylene

0.82 "9.6

92.9 826

113 '-86

0.9493 0.9349

6 020 4 060 v ^

49 35 ^

4.2

6.8

81

10 20 70 °

Example 6 to 15

A larger fluidized bed reactor was used in the following examples with a lower reaction section of 60 cm in diameter and 360 cm high and a top section 105 cm in diameter and 105 cm in height. The vortex-shaped resin bed the reaction section was 210-300 cm deep and was held by a 60 mesh stainless steel wire screen, which in turn was held in place by steel rods.

The reactor was prepared for use by filling it with clean, dry, finely divided polyethylene.

The bed's humidity and oxygen levels were by recirculating nitrogen or ethylene

one
80-90 C. and Entlüften.bis to / moisture content of 50-100 Teileipro Mill reduced. · The bed was further prepared by vortexing the finely divided polyethylene with nitrogen at 80-100 ⁰ C., with sufficient triethylaluminum to react with the all moisture and other traces of remaining toxin has been added. The nitrogen was then vented and the ethylene feed and then the catalyst feed to the side of the bed commenced, thereby initiating the reaction.

As the polymerization progressed, the original, finely divided polyethylene bed through the newly formed, polymerized Particles of the desired polymer replaced and withdrawn as part of the product. Gradually the bed became filled with the product formed from the monomer feed. For regulating the melt index and molecular weight hydrogen was used in many examples.

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-2A-

Examples 6 to 8 summarized in Table 2 show those produced by the above process in this reactor Polymers using the catalyst prepared in Example 1.

Examples 9 to 15 mentioned in Table 3 show productivity tests in a reactor with a diameter of 60 cm. Thereby, polyethylene was produced, with 100 ^a ß> ethylene at a surface mass velocity of 1590 lb / hr sq.ft. or 3.8 G- were introduced into a reactor which was kept at 100 ^° C. and a reactor pressure of 7 atmospheres.

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Example »

Table 2 Homopolymers

Mixed polymer 8

product

Melt index Flow rate Flow ratio

density

Stiffness; kg / cm ² tensile strength

Color - whiteness yellowness

co propylene content; G ew _, Tensile strenght; kg / cm

Polyethylene Polyethylene 0.18 0.98 26.1 73 221 75 0.9604 0.9643 9590 ■ 12 390 79 48 90 97 -1 -3 no no

Yield strength ; kg / cm elongation; $>

average reactor conditions

Temperature; oC. Pressure; kg / cm hydrogen content; Vol # propylene content; Vol- # ■ ethylene content; Vol-? £ G _{1 n} -P (surface mass velocity) production velocity; kg / h fiaum / time yield; lb / hr / cuft. Catalyst productivity; kg / kg

93 100 7th 7th 5.0 20th no no 95.0 80.0 3.5 3.5 25.9 26.3 2.3 2.3 1000 2000

Ethylene / propylene 0.31 39.4 127

0.9513 7210 74

89 -5

1.85 214.2 214.2 360

1.5

93.5

3.5

22.5

2.0

2000+

Tabel

Beiap. Bed duration d. Temp. Difference productivity

deep approach between gas in- formation speed.

m std outlet and outlet kg / std Ib per ^{hour 0} C. (ou.ft.)

kg of resin Temperature gradient
in bed; ⁰ C. g cat. 3 830 5 1700 9 2400 6th 1840 4th 1140 ro ώ 1050 VJl 1390

9 3 10.5 55

10 3 88 54

11 3 20 40

12 3 8 43

13 2.4 8 35 U 2.4 10 " 43

κ ».. 15 2.4 21 41

34.7 2.44 43.1 3.03 41.5 2.90 47.2 3.30 40.6 3.60 44.0 3.86 37.6 3.30

CD

cn

O CD

Example 1_6_ '

To demonstrate the effect of hydrogen on the melt index, ethylene was polymerized in the fluidized bed reactor used in Examples 2 to 5 in the presence and absence of hydrogen. Reactions were carried out atm at a pressure of 7 and a temperature of 11O ⁰ G. The results listed in Table 4 show that the hydrogen presence caused a Silylchromates as a catalyst in the vapor-phase of the fluidized bed reactor to increase the melt index in use.

Table 4

$ H ₀ Melt- Flow- Flow- Density Rigid-Tensile-Impact Basic- ^d index speed-lengthened. ₂ strength lare vis-

kg / cm health

0 , 7 0 , 00 3.5 e 1 - 17th 56 0 , 9659 10430 1 11 3 - 7th , 0 0 , 09 14th 1 53 0 , 9641 9730 1 29 2 , 5 8th e 0 , 26 40 1 0 , 9718 11410 56 , 9 B. i s P i

To show the particle size distribution of the product, a finely divided polyethylene product was prepared with the following Subject to the results of a sieve analysis:

Size distribution # of the product mesh

> 12: 2.6

^ • 12 > 20 10.3

^ 20> 40 23.3

^ 40> 100, 58.8.

4100 5.0

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- 28 Example 18

Poly (isobutylaluminum oxide) was made by adding 300

with milliequivalents of water slowly and / sufficient cooling and

thorough stirring to 300 milliequivalents of triisobutylaluminum, dissolved in 300 ecm hexane, added in a flask with constant flushing with dry nitrogen.

10 ecm of the poly (isobutylaluminum oxide) obtained were diluted to 500 ecm with hexane in a second flask under nitrogen. 120 micromoles of chromium 2-ethylhexanoate were added and the resulting solution was mixed thoroughly. The solution was then passed through a fluidized bed 10 cm in diameter containing polyethylene resin to a depth of 30-45 cm at virtually atmospheric pressure and fluidized by agitation and dry nitrogen. The nitrogen was not returned. The catalyst solution was added over about 20-30 minutes, the bed was maintained at about 60-70 ⁰ C. and stirred at 40 rpm by a running stirrer. The fluidization with nitrogen was maintained trocleiem W until the bed trookan'war, as indicated by its temperature.

The resin containing the dry, dispersed catalyst was then maintained under nitrogen pressure until used.

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Example 19

To prepare poly (i3obutylaluminum oxide), 960 ecm of a solution containing hexane and triisobutylaluminum in a concentration of 1 mol of triisobutylaluminum per 1 solution were first placed in a 2-1 flask which was jacketed for cooling and flushed with dry nitrogen . Then was added to the mixture temperature below 35 ⁰ C. to hold, 960 millimoles water slowly with vigorous stirring and cooling.

1000 g of a silica carrier described in Example 1 were extracted from under a blanket with stirring to 3 »0 1 isopentane

dry nitrogen in a 5-1 flask fitted with a stirrer and a sintered glass filter at the bottom. Then 120 millimoles of chromium 2-ethylhexanoate dissolved in hexane were added, whereupon the polyisobutylaluminum oxide was added. It was stirred for a further 20 minutes. The solvent was drained through the sintered glass filter and tested. It was found to be practically free of aluminum and chrome. The residue was warmed slightly, and it was passed slowly dry nitrogen, was until a free-flowing, substantially dry, powdery supported catalyst obtained.

The following examples illustrate the preparation of Olefin polymers in a fluidized bed reactor using the powdery, fine prepared in Examples 18 and 19 split catalyst

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Example 20 to 24

A jacketed experimental reactor similar to the accompanying drawing with a reaction section with a ratio from diameter to height of about 1: 7, ^ and an upper section with a diameter to height ratio of about 1: 2 was used to determine the types of polymers with the fluidized bed reactor according to the invention and the catalysts of the invention can be prepared.

The reactor was operated as usual at a pressure of about 7 kg / cm and at a gas flow rate between 3 and 4 ^G mf. At temperatures of 90 to 110 ⁰ C. · homopolymer were produced, while the production of copolymers at 8O ⁰ C. and was carried out under it. Hydrogen was used to regulate the melt index.

The polymers produced in this reactor are shown in the table 5 listed.

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co c *>

Table 5 108 21 22nd Copolymers 24 I. 1795 ' Homopolymers 7th Poly
ethylene Poly
ethylene 23 Ethylene /
Propylene * O
CD example 20th 5.5 1 2 Ethylene /
Propylene 1 product Poly
ethylene 94.5 6.0 0.08 2 1.1 Catalyst, here
according to the example above 1 - 306 20.3 0.05 67.6 Melt index 0.51 51 254 17.3 62 Flow rate 41.1 0.9502 0.9657 346 0.926 Flow ratio 81 8480
49 10 430
63 0.9556 3200
97 density 0.9559 62
4th - 6510
76 -. Stiffness; kg / cm ²
Additional strength 8750
90 - - 6.3 Color - whiteness
Yellowness - 2.5 > 504 'Propylene content - ) 504 Praying break resistance; hours - 107 83 82 average reactor conditions 7th 7th 73 7th Temperature; ⁰ C. 0.3 4.9 " 7th 10 Pressure; kg / cm 87 95.1 5 5.5 Hydrogen content; VoI- ^ - ■ - 85 35 Ethylene content; Vol- # 10 Propylene content; Vol- $

Example 25

For the production of an ethylene / propylene copolymer was a fluidized bed reactor with a lower reaction section 60 cm in diameter and 360 cm in height and an upper section 105 cm in diameter and -105 cm in height are used. The eddy-shaped resin bed in the reactor section was 210-300 cm deep and was carried through a 60 mesh stainless steel wire screen, which in turn was held in place by steel rods.

The reactor was filled with the one in a previous experiment manufactured clean, dry, finely divided polyethylene prepared for use. The moisture and

Oxygen content of the bed was reduced by re-circulation of nitrogen or ethylene at 80-90 ⁰ C. and venting to 50-100 parts per million. The bed was further prepared by vortexing the finely divided polymer with nitrogen at 80-100 ⁰ C., with sufficient Triäthylaluminiflm for reaction with the total moisture and other remaining acid was added to poisons. The nitrogen was then vented and the monomer charge and then the catalyst charge started, thereby initiating the reaction.

The catalyst was introduced from a storage container under a nitrogen blanket to the side of the reactor and through the impinging monomer stream is carried along in the fluidized bed.

209811 / U33

As the polymerization progressed, the original, finely divided polyethylene bed through the newly formed, polymerized Replaced ethylene / propylene polymer particles and stripped off as part of the first product. Gradually filled up I got the bed of the product formed from the monomer feed. To regulate the melt index and the molecular weight hydrogen was used.

The working conditions and properties of the polymer were as follows:
Polymer properties

Melt Index 0.40, Flow Rate '40.7

.! Flow ratio 102

Density 0.958

Stiffness; kg / cm ² 9380

Tensile Strength 42

Propylene content; Wt. # 1.42

Tensile strenght; kg / cm ² ■ 257.25

Stretch limit; kg / cm 257 »25

Strain; $ "65

Hydrogen content; vol ~ # 1.5

average reactor conditions ™

Propylene content; Vol .- # 3

Ethylene content; Vol - # - 95.5

G- (surface mass ^velocity 4.2 mx in bed)

209811 / U33

Example 26

To show the particle size distribution of the product, the one prepared with the catalyst of Example 19 was Subjected a cut polyethylene to sieve analysis with the following results:

Distribution of the particle size $ of the product mesh . ______

> 12 4.1

-12> 20 50.1

^ 20> 40 41, 0

Z40> 100 4.5

ZJOO 0.3

209811/1433

Claims (1)

Patent claims 1, - Continuous process of making solid, fine fertilize divided polymers from olefinically unsaturated compounds, characterized in that at the same time: (a) a gaseous one containing a polymerizable olefin Stream with a powdery silyl chromate or poly (hydrocarbyl aluminum oxide) complex polymerization catalyst for the olefin in a polymerization zone consisting of a fluidized Bed of the formed and forming polymer particles exists, with one to maintain a complete Swirling sufficient mass gas flow rate and bringing the solid polymer particles into contact at a temperature below the sintering temperature; (b) a small proportion of the fluidized bed from the polymerization zone withdraws as discrete particles in suspension with a portion of the gaseous stream; (c) withdrawing the unreacted portion of the gaseous stream from the polymerization zone; (d) the unreacted gaseous stream for removal the heat of reaction cools; (e) the cooled gaseous stream below the base of the fluidized bed a at one to maintain fluidization returns to the polymerization zone at a sufficient rate 2. - Method according to claim 1, characterized in that the mass gas flow rate through the bed is about 2 to 6 G ~, 20981 1/1433 T / 95109 is preferably about 3 to about 5 G _f) . 3.- The method according to claim 1 and 2, characterized in that the fluidized bed is at a temperature below 110 ⁰ C.
is held. 4.- The method according to claim 1 to 3, characterized in that the silyl chromate catalyst is on a porous support from the group of alumina, silicic acid, zirconia and thore earth with a particle size below about 250 microns. 5 - method according to claim 1 to 4, characterized in that that the SiIy teaching omatkatalysat or a Bistriarylsilylchroinat, is preferably Bistriphenylailylchroiiiat. 6, - method according to claim 1 to 4> characterized in that the poly (hydrocarbyl aluminum oxide) poly (isobutyl aluminum oxide) is. 7.- The method according to claim 1 to 6, characterized in that that hydrogen is used as a component of the gaseous stream will. 8.- The method according to claim 1 to 7, 'characterized in that ethylene is a component of the gaseous stream. 9, - method according to claim 1 to 8, characterized in that that propylene is a component of the gaseous stream. Of the. Patent attorney: 20981 1 / U33