FI76354B - CATALYTIC COMPONENT FOER ZIEGLER-NATTA CATALYST OCH FOERFARANDE FOER POLYMERIZERING AV -OLEFINER. - Google Patents

Description

76354 1 Catalyst component for Ziegler-Natta catalysts and process for the polymerization of oi-olefins Catalyst component for Ziegler-Natta catalysts and for the preparation of polymer olefins 5

The invention relates to active catalyst components useful in the Ziegler-Natta family of catalysts capable of polymerizing cis-olefins containing at least 3 carbon atoms. The invention also relates to a process for the preparation of active catalyst components for the polymerization of o-olefins having at least 3 carbon atoms. In one aspect, the invention also relates to a polymerization process using the active catalyst components of the invention.

In the polymerization of olefins using so-called Ziegler-Natta catalyst systems, transition metal compounds are used as essential catalyst components. The preparation of these latest generation catalyst components typically involves the reaction of a metal halide such as magnesium chloride or an adduct of magnesium dichloride with two or three moles of alcohol with a titanium halide compound such as titanium tetrachloride in the presence of Lewis bases as the electron donor compound.

This invention relates to catalyst components prepared from chlorine-free organomagnesium compounds, a chlorine-free silanol compound and a titanium halide compound.

The prior art includes descriptions of catalysts obtained by treating magnesium alkyls with silanol or silane compounds and transition metal compounds under various conditions. For example, according to U.S. Patent 4,525,557, ethylene can be polymerized using a catalyst system containing a transition metal component prepared in three steps: first the magnesium dialkyl compound is reacted with a silanol compound, then the reaction product is treated with trichlorosilane and finally the titanium halide is treated.

76354 2 1 This catalyst has been used only for the polymerization of ethylene and the reaction with the silane compound and the magnesium compound has been carried out at room temperature. The catalysts described in this patent are not suitable for polymerizing propylene or other olefins.

U.S. Patent 4,335,016 prepares a catalyst component for polymerizing ethylene by first reacting a porous support material such as silica with an alkylmagnesium compound and then the resulting product with a silane which is hydrocarbyloxohydrocarbylsilane. The catalyst described in these 10 patents is also not suitable for polymerizing propylene.

EP-A-104 374 prepares a catalyst component by reacting an arylsilanol with a halogenated transition metal compound such as titanium tetrachloride and then reacting the resulting product with an organomagnesium compound. This catalyst component has been applied to the surface of the particulate support and has only been used to polymerize ethylene.

We have now found that the catalyst components prepared according to EP-A-104 374 do not give active Ziegler-Natta catalyst components when used in the polymerization of propylene. The reason for this was found to be the relative order of the preparation steps and the reaction conditions. Claim 1 of said EP specifically states that the first step is the reaction of a silanol compound with a titanium halide and then the reaction product is reacted with an organomagnesium compound. In addition, the reaction with the silanol compound is carried out at a low temperature, preferably at room temperature. In our experiments, we have found that the catalysts prepared in this publication are not suitable for the polymerization of propylene and other οί-olefins.

In accordance with the present invention, we have found that in order to obtain active catalyst components for the polymerization of propylene, it is necessary to reverse the order of the preparation steps 35 of EP-A-104 374 and to use substantially higher temperatures during the reaction with the silanol compound. The invention thus relates to a catalyst component used in unsupported Ziegler-Natta 3 76354 l catalyst mixtures for the polymerization of C 1-4 olefins having at least three carbon atoms, said catalyst component being obtained by treating a chlorine-free organomagnesium compound with solid hydrane groups containing one or two then with titanium halide compounds and the invention is characterized in that said treatment of the organomagnesium compound is carried out first by treatment with said silane compound at a temperature of 60-110 ° C and then with the titanium halide compound optionally together with an electron donor compound.

10

The organomagnesium compound of the invention does not contain halogen atoms. Suitable magnesium compounds include magnesium dialkyl compounds such as ethyl butylmagnesium, dibutylmagnesium, diisobutylmagnesium, dihexylmagnesium, dioctylmagnesium, dideylmagnesium and propylmagnesium.

Preferred magnesium dialkyls are ethylbutylmagnesium and n-butyl-4'-methylpropyl-magnesium + diethylmagnesium.

Silanol may contain one or two hydroxyl groups and does not contain chlorine atoms. Thus, the silanol compound is an organically substituted silane-20 diol or silanol. The substitution group is an aromatic, preferably phenyl group. The most preferred silanols are diphenylsilanediol and triphenylsilanol.

The reaction between silanol and magnesium alkyl appears to attach 25 magnesium alkyl to the silane atom via an oxygen bridge, for example "-Si-O -MgR '-". In the second step, a substitution between magnesium alkyl and titanium chloride appears to occur with the formation of a compound of the form "Si-O-TiCl 2" which is soluble in excess titanium tetrachloride. The reaction time is quite short, from a few minutes to a few 30 hours. Importantly, the temperature is relatively high, namely above 60 ° C, preferably 60-110 ° C. The molar amount of the magnesium compound is preferably lower than the molar amount of the silanol compound when magnesium dialkyl and diphenylsilanediol are used.

The titanation is carried out at a temperature of 60 to 110 ° C, preferably 80 ° C.

4 76354 1 During titanation, a so-called internal electron donor compound (Lewis base) can be added to the catalyst component. This improves yield and isotacticity. Suitable donors include esters of butyl and phthalic acids and hydrosilane derivatives. The preferred donor is diisobutyl 5 phthalate.

The particles of the catalyst component of the present invention have the form of diphenylsilanediol or triphenylsilanol used in the preparation of the catalyst component. When the material of the starting silane derivative is crystallized as 10 needles, a needle-like catalyst is obtained, which is quite unusual. Due to this replication phenomenon, the catalyst produces needle-like polymer particles with good flow properties in the polymerization process.

The catalyst components according to the invention can be used for the polymerization of α-olefins having at least 3 carbon atoms. The catalyst components can be activated in a known manner by means of a cocatalyst such as alkyllithium, alkylmagnesium, alkylaluminum, ethylaluminum halide or alkylzinc. Activation can take place inside or outside the polymerization reactor.

In essence, the catalyst mixtures obtained in the simple and novel manner described above provide high yields and high isotacticity in the polymerization of o-olefins, preferably propylene and butene. Known modifications of the polymerization process are also possible, such as the addition of hydrogen to the monomer feed or to the polymerization reactor to modify the properties of the polymer, such as the melt flow index.

The following examples are intended to illustrate the invention.

30

Example 1

A catalyst component was prepared in a 700 ml glass reactor equipped with a stirring apparatus, temperature control and a nitrogen purge-35 system. To the reactor were added 20 g of diphenylsilanediol and 200 ml of dried (without air) heptane at room temperature and 69 ml of DBME (Dibutylmagnesium-E'S) Lithium Corporation of Europe Ltd, 5 76354 1 n-butyl-1-methylpropyl-Mg and diethyl-Mg mixture) of heptane solution (DBME content 9.94 g). The solution was added dropwise with stirring over about 15 minutes at room temperature. After all of the DBME was added to the silanediol solution, the temperature was raised to 95 ° C and maintained at this temperature for two hours. The slurry was then cooled to room temperature and stirring was stopped. After siphoning, 200 ml of heptane were added under a stream of nitrogen and with stirring. Thirty minutes later, stirring was stopped and the diluent was removed. This washing operation was repeated twice. After the last heptane removal, 250 ml of titanium tetrachloride were added at room temperature. The color of the slurry changed slightly from white to brown. 1.95 g of DIBF (diisobutyl phthalate) were then added dropwise. The temperature was raised to 80 ° C, where it was kept under stirring for two hours.

15 The settling of the slurry after the mixing was stopped was very fast. The liquid was removed by siphoning and 250 mL of TiCl 4 was added. The slurry was kept under stirring at 80 ° C for two hours. The liquid was then removed as above. Finally, the product was washed with heptane. Two treatments were performed with 250 ml of heptane for two hours at 80 ° C and three more times at room temperature.

A 2-liter polymerization reactor containing 1300 ml of dry heptane was charged with 30 mg of a catalyst system pretreated by stirring with heptane with an Al-alkyl compound (triethyl-Al) and diphenyldimethoxysilane as a Lewis base (external electron donor). The molar ratio of Al to donor was 10: 1 and the catalyst component was prepared as described above. The Al: Ti ratio was 200: 1. Propylene was polymerized under the following conditions: partial pressure of propylene 9.7 bar, partial pressure of hydrogen 0.3 bar, temperature 70 ° C and polymerization time 3 hours.

The composition and properties of the catalyst component and the properties of the obtained polymer are shown in Table 1.

35 6 1 Example 2 76354

A catalyst component was prepared as in Example 1 except that butyloctylmagnesium was used as the alkylmagnesium compound. Pro-5 pen for polymerization as in Example 1. The composition and properties of the catalyst component and the resulting polymer are shown in Table 1.

Example 3 A catalyst component was prepared as in Example 1 except that the reaction between silanediol and alkylmagnesium was performed at 60 ° C. Propylene was polymerized as in Example 1. The composition and properties of the catalyst component and the resulting polymer are shown in Table 1.

15 Example 4

A catalyst component was prepared as in Example 1 except that the reaction between silanediol and alkylmagnesium as well as titanation was performed at 60 ° C. Propylene for polymerization as in Example 1.

The composition and properties of the catalyst component and the resulting polymer are shown in Table 1.

Example 5 A catalyst component was prepared as in Example 1 except that the reaction between silanediol and alkylmagnesium was performed at 60 ° C and titanation at 110 ° C. Propylene was polymerized as in Example 1. The composition and properties of the catalyst component and the resulting polymer are shown in Table 1.

30

Example 6

A catalyst component was prepared as in Example 1 except that triphenylsilanol was used as the silane compound. Propylene was polymerized as in Example 1. The composition and properties of the catalyst component and the resulting polymer are shown in Table 1.

1 Example 7 7 76354

A catalyst component was prepared as in Example 3 except that triphenylsilanol was used as the silane compound and no internal donor was used. Propylene for polymerization as in Example 1. The composition and properties of the catalyst component and the resulting polymer are shown in Table 1.

Example 8 1-Butene was polymerized in the gas phase in a 2 L reactor with a viewing window and a spiral mixer using polypropylene (30 g ICI GW 521E) as the fluidized bed material. For prepolymerization, 51.4 mg of the transition metal catalyst component of Example 1 with 0.017 mmol of titanium, 863.2 microliters of triisobutyl Al cocatalyst with 3.4343 mmol of aluminum and 39.2 microliters of diphenylmethoxysilane as an external donor were charged to the reactor. , wherein the molar ratio of Al: Ti was 200: 1 and the molar ratio of aluminum to donor was 20: 1. The mixture was then heated to 45 ° C whereupon the pentane evaporated in about 10 minutes. The reactor was cooled to room temperature and butene was introduced into the reactor at a partial pressure of 2 bar and nitrogen at a partial pressure of 3 bar. The prepolymerization took place in 30 minutes at 30 ° C with a stirrer speed of 750 rpm.

For the actual polymerization, the temperature was raised to 55 ° C and the butene-25 partial pressure to 5 bar. Hydrogen was fed at a partial pressure of 0.1 bar. The agitator speed during the polymerization was 900 rpm.

73 g of polybutene having an isotacticity index of 96.8% were obtained as the product of the 3.0-hour polymerization, so that the activity of the catalyst was 1.4 kg of PB / g of catalyst, i.e. 89 kg of PB / g of Ti.

35 8 A * 76354 q co I CO 2

cO 4-1 φ m cm O

iH J-ι T3 · * ·> * *

3 'Η q cm cm O

CO> «Η CM -Η ΓΊ co

C/O

3 (0

•B

4J "H

C/O

CO ^ 4-> a> cm cm m o o m oo Ο Ό * * * * * * co q -o * oo r ^ ·. oo oo oo m o> σ> & σ> σ> σ \: co

: co · Η • H 4J CO M 4J

q φ in q 0 | in

CO S i — I

• h En co

> iH 4J

• H o «0 h o- ^ <r —iom 4-» o «n - * v £> cm mo ^ ϋΟ 00 · * · * ^ ·» ^ · * <j \ cr * mm n- - <f cn en tn oo · - '* —14 CM * “* 4 O Λ ^ ¢ 3 * H * *> * ^ ·>

• H CO 5-5 O '—i O O V O

4J

q

(D O

q r-- o o o o o * Q a A M · «« s M n O, r-t vo r -'- cn oo cn vo nt —I E U fc ^ s -d "<f is n) · m Nt <n 0

O

* 6 $ Ή '' “N

M «to o oo ό cn —i en nt m 3 4J 3 Ή« »·· >> ·>« ® rH En 0 H & - «n n -i cn cn m f- ~. cn 3>, 3 o CO Ή 4J 'H tOtn u · »vo Γ". — i in -j- σ> esi 4JO *> ·> *. ·. »** C) 0

m o oc S

^ 2 ^ $ »· § ι-H i — I» -H r-H i-H ι-H CO

σ> Ä

mf

CJ

ÖO ^ * H

S θ Ή 1 li q o

* H 4J »H * H

iH O Ipd) CO TJ

in O ^ oi * h ίη ω q w w q q q -h

^ S PQ S I 00 CO rH

»H PQ ÖO PQ CO CO O

<osp = = = = e e ή e 3 iH -H tfl

• H t — f CD i — I

CD En Ή * H

CU En * H CD

CN C XJ> v -H

/ -n 60 M En rH

M «O C>, • H O * S -H (U En

C 'O i-t ι-t c * -i C

CO Ή Ή r-l En * H 04 «en en En En Q ^

r-C cn m En 4J iH

• H Ä -3 4-1 3 II tJ

en ® r = = = ® r 3 «H

®l (N

• H li Il

Q EC

4-10®

• H II U '-z O

J4 O · Η Ή I -li ω 3 cn en • h> -igm cn en en ai eQ 60 ® -e WB —i cn en -o- m ό rn qg ex ®, 76354 1 Comparative Example 1 of EP-A-104 374 following the procedure on page 10, the following polymerization experiments were performed with or without the use of 5 electron donors. Ph 2 SiOH was treated with B0MAG (= butyloctyl-magnesium) in a 1: 1 molar ratio in a heptane solution (about 5 g of components in 100 ml of heptane) for 2 hours at room temperature. The excess solvent was then siphoned, excess TiCl 2 was added and stirred for 15 minutes at 100 ° C. The liquid was siphoned off and the precipitate was washed 3 times with 10 heptane. The TiCl 2 treatment was performed only once. The polymerization of propylene was carried out as described in Example 1. The results are shown in Table 2.

Table 2 15

Kata- Catalyst element Electron- Catalyst catalyst composition /% donor activity no Ti Mg Cl Si kg PP / g cat 20 _ 1 6.4 7.4 37 0.14 - 0.83 2 4.9 3.7 39 0, 15 - 1.32 3 10.0 8.1 48 0.17 ethylbenzo-0.41 4 6.7 6.2 35 0.8 agate 0.02 mol 0.50 25 _

Comparative Example 2 Catalyst No. 130 shown in Table I of EP-A-104 374 was applied to the polymerization of propylene.

The catalyst component was prepared as follows: 0.07 mol of Ph 2 SiOH was treated with 100 ml of toluene, after which 5.5 g of silica (Davidson 952) was added. The silica must be treated at 700-800 ° C. To the mixture was added 0.07 mol of BOMAG (20% heptane solution). The mixture was stirred for 2 h at room temperature. 250 ml of 10 76354 l of TiCl 4 were added with stirring. The temperature was raised to 95-100 ° C for 10 min. The mixture was allowed to cool to room temperature, and the resulting product was washed three times with heptane to remove excess TiCl 4. A catalyst component was obtained with elemental concentrations: Mg = 1.8 Z, Ti = 2.7 Z, Cl = 13.7% and Si = 14.2%.

When this component was used to polymerize propylene by the method of Example 1, the activity of the catalyst was 0.32 kg PP / g cat.

10

Comparative Example 3

According to Example VII of U.S. Pat. No. 4,525,557, the catalyst component was prepared as follows: 2.7 g = 12.5 mmol of Ph 2 SiOH in 60 ml of heptane was treated with 36 ml of B0MAG (= 25.7 mmol) at room temperature for 2 hours. TiCl 2 was added dropwise 2.38 g = 12.5 mmol in 10 mL of heptane to form a dark precipitate immediately. The slurry was stirred at ambient temperature for 2 hours, washed 3 times with 30 ml of heptane, and dried in vacuo. The elemental composition 20 of the obtained catalyst component was Mg = 7.6%, Ti = 7.8 Z, Cl = 21.8 Z and Si = 2.84 Z. When using this catalyst component in the polymerization of propylene, it was found that the activity of the catalyst was approximately 0 kg PP / g cat.

25 30 35

Claims (7)

A catalytic component used in Ziegler-Natta type catalytic compositions without a binder for polymerizing o -olefins of at least 5 carbon atoms, said catalytic component being obtained by treating an organic magnesium compound which does not contain chlorine with solid silane compounds containing or two hydroxyl groups and titanium halides, characterized in that said treatment of the organomagnesium compound is carried out by first treating said silane compound at a temperature of 60-110 ° C and then with a titanium halide compound selectable together with an electron donor compound. 1 Patent claim A catalytic component according to claim 1, characterized in that said organomagnesium compound which does not contain chlorine is a dialkylmagnesium compound, wherein the alkyl groups are the same or different and contain from 2 to 10 carbon atoms. Catalytic component according to claims 1-2, characterized in that the silane compound containing said one or two hydroxyl groups Mr selected from the group diphenylsilanediol and triphenylsilanol. Catalytic component according to any one of claims 1-3, characterized in that said titanium halide is titanium tetrachloride. A Ziegler-Natta catalytic composition without supports for polymerizing oC-olefins of at least 3 carbon atoms, comprising (1) a catalytic component obtained by treating an organomagnesium compound which does not contain chlorine with solid silane compounds containing one or two hydroxyl groups and 2) a cocatalyt selected from the group of alkyl lithium, alkylmagnesium, alkylaluminum, alkylaluminum halide or alkylzinc, and (3) optionally an external electron donor compound, characterized in that said treatment of the organomagnesium compound has been carried out by first treating with said silane compound at a temperature of 60-110 ° C and then with a titanium halide compound selectable together with an electron donor.