CS259736B1 - Catalyst for 1-alkenes polymerization and copolymerization - Google Patents

Abstract

The present invention relates to a catalyst for polymerization and copolymerizing 1-alkenes. On porous silicon oxide and / or aluminum containing 0.3 to 3 mmol / g of surface OH groups, at least one aluminum compound is applied general vzords (I), then at least one a titanium compound of formula (II) a finally, at least one magnesium compound of formula (III) wherein R 1, R 2, R 3, R 4, R 5 are alkyls of 1 to 10 C atoms or aryls, wherein R 2 and / or R 3 may also be halogen, hydrogen or alkoxide OR 1, k is 1, 3, 1, m, r, s is 0 to 2, with k + 1 + m = 3, r- (- -j- s = 2, X, Y are halides, and alkoxides with R 1, cyclopentadienyls wherein X 2 can be oxygen, p, q are 0 to 4, with p -j- - | - q = 3 or 4 in molar ratios of 1 / / OH carriers 0.1 to 10, II / I to 100, III / II 0.5 to 20. Al R ^ R ^ Rm3 (AND) TiXpYQ (Π) MgRr4Rs & (III)

Description

The present invention relates to supported catalysts for the polymerization and copolymerization of 1-alkenes in which oxides are used as the support. Contemporary catalyst systems for the polymerization of 1-alkenes have already achieved considerable perfection. In particular, the introduction of supported catalysts, which increasingly utilize a catalytically active metal, enables relatively high activities to be achieved - more than 3,000 kilograms of polymer / g catalytic metal. MPa. h. Transition metal catalyst systems are widely used and exhibit good copolymerization parameters in addition to high activity. They are compounds of the general formula:

M _m M * X _2ni Y. _nE where

M = Mg, Mn, Ca

M ‘= Ti, V, Zr

X = Cl, Br, J

Y = halogen, —OR, —SR, —NR 2, where R is alkyl, m = 0.5 to 2 n = 0.25 to 40

E = electrodonor (ether, alcohol, ester)

Activation of the catalyst is carried out directly in the polymerization reactor, most often by organoaluminum compounds. Catalysts of this type are described, for example, by Karol in US 4,302,566, Stevens in US 3,787,384, Strobel in US 4,148,754, Ziegler in US 4,063,009, and Graft in US 4,173,547. Other titanium compound carrier catalyst systems are described in GB 1,484-254, DT 2,809-272, BE 884-513, GB 2,099-834 and US 4,490-514. A common feature of these systems is the interaction of the inorganic carrier with the organomagnesium and / or organoaluminum compound followed by the interaction with the transition metal compound. Immediately prior to the polymerization or up to the reactor, the organoaluminum component is activated, requiring large quantities of organometallic compounds to be introduced into the reactor, leading to more complex control of the polymerization process, and may result in more frequent sludge formation in the reactor.

Especially in the case of gas-phase polymerization of 1-alkenes using transition metal catalysts IV. and group V and group of the Periodic Table of the Elements, feeding the organoaluminum compound into the reactor is a source of unpleasant technological problems. Due to traces of oxygen and moisture, the walls of the reactor and other equipment are coated with alumina, which is a strong adsorbent of impurities causing catalyst deactivation. These are removed again by reaction with organoaluminium compounds, further aggravating the problem. A process for preparing single-phase, multi-component catalysts that do not require activation by an organometallic in the reactor and do not have the aforementioned negative properties has been described in AO No. 256 961.

Some patents disclose the preparation of supported catalysts based on titanium compounds, first treating the silica surface with phosphorus compounds (US 4,510-299), inorganic sulfur compounds (J5,000-880) or an organic silicon compound (DE 3,228-065) ), after which the carrier thus treated (largely devoid of reactive hydroxyl groups) is only reacted with the organometallic compound and then with the transition metal compounds. Certain patents (BE 866-957, DT

721–194, DE 3 404–668, BE 845–983, BE 857–100, US 4,446–288, BE 846–450, DE

228-065) describe the deposition of the reaction products of organometallic compounds with polar and non-polar solvents (alcohols, ethers, esters) onto a carrier, thereby changing the surface layer of the carrier without these reaction products forming an active part of the polymerization center capable of alkylating and reducing the transition compound. metal.

BE 866-420 and J5 4138-887 disclose the preparation of a non-carrier catalyst for solution polymerization. Although, according to them, a single-phase catalyst is formed, it is not suitable for gas-phase polymerization because it does not have a suitable particle distribution.

The disadvantages of said supported catalysts are overcome by the catalyst according to the invention.

SUMMARY OF THE INVENTION The present invention provides a catalyst for the polymerization and copolymerization of 1-alkenes, which is obtainable by contacting a support of silicon and / or aluminum with a particle size of 1 to 1000 μΐη with a pore volume of 0.3 to 3 cm ³ / g A surface area of 100 to 1000 m ² / g containing 0.3 to 3.0 mmol / g of surface OH groups is applied in a hydrocarbon solvent or vapor phase at a temperature between freezing point and boiling point of at least one compound of the formula I

AlR _k ¹ R ¹² R m ³ (I) then at least one titanium compound of formula II

TiXpY, (II) and finally at least one magnesium compound of formula (III)

MgR / R / (III) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ are alkyl of 1 to 10 carbon atoms or aryl, wherein R ² and / or R ³ may also be halogen, hydrogen or an alkoxide OR ¹ , k is 1 to 3,

1, m, r, s is 0 to 2,

259738 where k + 1 + m = 3 and r + s = 2,

X, Y are halides, alkoxides, cyclopentadienyls, wherein X 2 may be oxygen, p, q are 0 to 4, wherein p + q = 3 or 4, in the J / OH carrier molar ratios of 0.1 to 10, II / I 1 to 100, ΙΙΙ / ΊΙ 0.5 to 20.

The carrier for the preparation of the catalyst of the invention is silica or silica / alumina, which is dehydrated at temperatures of 200 to 900 ° C by air and / or nitrogen in a fluidized bed for at least 4 hours. The silica thus treated contains 0.5-3 mmol of OH groups per g, depending on the dehydration temperature.

The preparation of the carrier catalyst according to the invention can be divided into several phases:

Interaction of the reactive sites of the carrier with one or successively with several organoaluminum compounds. Reaction products are formed firmly fixed to the support surface. The molar ratio of the sum of the organometallic I to the OH groups of the support is in the range of 0.1 to 10, preferably 0.5 to 1.0.

2. Interaction of the support prepared according to item 1 with one or more of the compounds II The titanium compounds are firmly anchored on the support and reacted with the fixed reaction products of item 1. The molar ratio of the sum of organo-clay compounds I to the sum of compounds II is maintained 1 to 100, preferably 5 to 20.

3. Interaction of the carrier prepared in steps 1 and 2 with one or more organomagnesium compounds III. The molar ratio III / II is maintained in the range of 0.5 to 20, preferably 1 to 8. The organomagnesium compound is anchored in the surface layer of the carrier particles, and does not diffuse into the interior of the particles during the preparation and storage of the catalyst. This accumulation of the organomagnesium compound on the outer surface of the carrier particles has a beneficial effect on the stability of the active center against the potentially inactivating action of strong electron donor compounds, which are usually in trace in the feedstock or may come into contact with the catalyst during preparation, storage and transport.

Said operations are carried out in a hydrocarbon suspension within the temperature range determined by the freezing point and the boiling point of the hydrocarbon used, preferably at temperatures between 20 and 40 ° C, or, depending on the physical properties of the components used, also by direct contact of the component with the carrier. The presence of electron donor solvents such as alcohols, ethers, esters in excess of trace amounts is undesirable.

By successive interaction of the individual components of the catalytic system according to items 1 to 3, an active polymerization center with an optimal ability to polymerize 1-alkenes is formed. By fixation of the components on the carrier their migration is prevented and thus they do not give rise to side reactions leading to the disappearance of the active centers.

The catalysts prepared according to the invention have a number of advantages over the prior art catalysts: they retain high activity even after prolonged storage, they provide excellent granulometric product composition and high bulk density, while avoiding alumina build-up on the inner walls polymerization reactor. By suitably selecting the components and conditions for preparing the catalyst, the kinetics of polymerization (such that remelted slices are not formed at high speeds), mean molecular weight, molecular weight distribution, and morpholigy of polymer particles can be easily controlled over a wide range.

The following examples illustrate the invention. The ratios in the examples are molar.

Example 1

General procedure for preparing catalysts

In a dried 100 ml glass reactor, 50 ml of dehumidified hydrocarbon (e.g. heptane), dehumidified with water and oxygen, are charged, and 5 g of activated activated nitrogen stream at 200 DEG to 900 DEG C., a solution of organic aluminum compound of formula I or a mixture thereof in a hydrocarbon, and the mixture is stirred at room temperature for 10 minutes. One or more titanium compounds of the formula II (preferably in the form of a hydrocarbon solution) are then added and allowed to react at room temperature with stirring for 30 minutes. Finally, a solution of an organic magnesium compound of the formula (ΙΓΙ) or a mixture thereof in a hydrocarbon is added. After 30 minutes, the product was freed of solvent (e.g., by evacuation). The resulting beige powder can be used as a catalyst for fluidized bed polymerization.

Example 2

The 1 L glass reaction vessel is equipped with a spiral stirrer that allows perfect intensive mixing of bulk materials. 300 g of the carrier activated in a stream of N 2 at 200 to 900 ° C for 4 hours are poured into a nitrogen-dried vessel and stirring is started. The ultrapure nitrogen is fed through a glass frit to the bottom of an 80 ml vaporizer vial and bubbled through a solution of organoaluminum component I or mixtures thereof in a hydrocarbon (e.g. hexane) and is fed through the bottom of the reaction vessel into the activated support layer. evaporating the organoaluminum compound solution into the evaporation vessel, titanium compound II or a mixture thereof (preferably in a hydrocarbon) is introduced into the reaction vessel in the same manner. Finally, an appropriate amount of organomagnesium compound III or mixtures thereof is metered into the evaporation vessel and allowed to evaporate The evaporation of the compounds I-III can be significantly accelerated by heating the vaporizer. The individual reactants I-III can be dispensed into the vaporizer vessel cleanly or as solutions in hydrocarbons. Catalyst maintained by external cooling at room temperature, a slight increase in temperature by reaction heat to 60-80 ° C is not a problem. A free-flowing white to beige powder is obtained which can be used directly for polymerization in a fluidized bed reactor.

All handling of the activated carrier and the I-III substances must be carried out in an ultra-pure environment, preferably under a stream of ultra-pure inert gas (nitrogen, argon) containing <1 ppm H2O and <1 ppm O2.

Example 3

The catalysts were tested by polymerizing 1-alkenes in a laboratory 1.5 L discontinuous fluidized bed reactor, which allows the preparation of 250 g of polymer and / or on a pilot plant continuous fluidized bed reactor with a productivity of 25 kg polymer / h. The different catalyst compositions and polymerization test conditions are shown in Tables 1 and 2.

239736

Table 1:

Examples of catalytic systems for polymerization of 1-alkenes

Pore. No Catalysts - I1 / I2 I / OH II II1 / II2 I / II III ΙΙΙ1 / ΙΠ2 - III / II

ΟτΗγΗΟΟγΗτΗγΗΝ

Hooin CM CM r-s < N

CQ bo

CQ & 0 p

3333333333 ζ- _M

4_.4 _. + - 4-.4-4 -. + - 4 - + - 4 -. ”Snmn WWWWWWWWWWKK £££ JOMSúúOOOOMMMMMMMMMMM

1313 ~ iQiq m exit-? O T-i C \ T 13 O 13 C \ f TT Til 13 13 O

CM 13 (3

O »rM

H

I.E. -T * it

S-i «

^ nil ^ OOO ^uu HHHhH S υδδυ ^ οο aaaa as ^ ρΡπί-Κ ^ ΗΗυυϋμϋΗ

13 05 o CO o 'o rH

T-1 rl Η Η Η H

HN-H

Steed!

ω * f ffi W sSes <C4 cm r — H

O

-ffi cm β

it

4- »w

CM wwwSww cw £ o- ff ww ^ -4 ρ — 1 ^{- -} 4 ρ— <p — 4 | —1 P “^ P — 4 P ^- <f — 4 Γ” ^- * <<<<<<<<:<<<<<<<

β

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Οη

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r — I o

and a

H rj H

O \ t> - l · - t> t> 4 bx tm cm o θ 'σ' <=> * σ 'σ σ' σ ο τ

T-JCMCO ^ mCDt ^ COCXOrHCMCO ^ in _Ι _I _I _I _I _I ο

CM «“ Η

C> φ β

»* 4 a

r — 4

Honors «π4> ο ο

τ3 ο

CX.

> 4-α

4—>

ω

Ο

Ρ ρ2 \ ^ 3

Ά χί

C μ cn 3

P i φ φ> 4-4 honors • 4-4-4 f-i &

β,

Φ> honor £ honor * 2. & Β ^Λ > É4 "

&Η & 4 r-1 0> Ν >> 4 ^ tíη κη κΰ

I — i honors> · and σ + - *

Rt rrt

Honors' Honors O β N O Pm

Φ

4- * β

Í4

On

honors β

N>

>>

f-4 'Honor

N ^ 5> β

Φ

WITH

Honors

í — í ρβ 4-J 05 _ O.>, 2 x í >> ρ — 4 + - Ν Φ and AND 4- » Λ β 4-J È4 2 ϊ *. * ⁵ β Φ ο β Φ Φ & V i 9-4 | pQ 1 ω i i ! x 1 4- * 1 + -> 3 ^and 2 Λ Λ! Μ with and ω ρ X Ď4 Ο AND"

Table 2:

Tests of polymerization of 1-alkenes on a catalyst according to the invention

Catalyst Partial pressures MPa H2 Temperature ethylene propylene 1-butene ° C

Time Polymer yield h

1 18 _ _ 2 90 _ 15 * 1 17 - 1 2 90 - 13* 2 18 - - 2 90 2 240 3 16 - - 4 90 2 140 4 16 - 2 2 80 3 230 5 16 4 - . - 80 3 180 6 16 - 2 2 90 2 260 7 18 - - 2 100 ALIGN! 2 200 8 16 - 2 2 90 2 240 9 18 - - 2 100 ALIGN! 2 230 10 16 2 - 2 80 3 280 11 18 - - 2 80 2 40 12 18 - - 2 80 2 30 13 - 18 - 2 80 4 20 May 14 - 2 16 2 80 4 8 15 Dec 18 - - 2 100 ALIGN! 2 25

Note:

The catalyst charge in the laboratory reactor was always 0.1 g. * - Productivity in kg / h obtained from the pilot plant unit

Claims (1)

Catalyst for the polymerization and copolymerization of 1-alkenes prepared by contacting a support of silicon and / or aluminum oxides with a particle size of 1 to 10,00 gm with a pore volume of 0,3 to 3 cm ³ / g, with a surface area of 100 to 1 000 m ² / g, containing 0.3 to 3.0 mmol / g of surface OH groups, is applied in the environment of a hydrocarbon solvent or in the vapor phase at a temperature between the freezing point and the boiling point of the deposited substances at least one aluminum compound of the formula AlR _k ¹ R, ² R _m ³ (I) then at least one titanium compound of formula II TiX _p Y _q (Π) Invention and finally at least one magnesium compound MgR of formula III, R ^4? (III) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ are alkyl of 1 to 10 carbon atoms or aryl, wherein R ² and / or R ³ may also be halogen, hydrogen or an alkoxide OR ¹ , k is 1 to 3 1, m, r, s is 0 to 2, with k - | -1 m = 3 and r + s = 2, X, Y are halides, alkoxides with R ¹ , cyclopentadienyl, wherein X 2 may be oxygen, p, q are 0 to 4, wherein pq = 3 or 4, in molar ratios I / OH of carrier 0.1 to 10, II / I to 100, III / II 0.5 to 20.