Method for producing mixed alcoholates of metals for catalyst of olefin polymerization

专利摘要:
Alkoxides of transition metals, selected from among tetravalent Ti, tetravalent and pentavalent V, tetravalent Cr and tetravalent Zr, actinides and lanthanides, are reduced to corresponding alkoxides of lower valency by reacting such higher valency metal alkoxides, in liquid phase, with vapors of metals of the alkaline earth group, the III group and the IV group metals and magnesium. Very efficient polymerization catalysts for the polymerization of unsaturated compounds are thus obtained.
公开号:SU1319782A3
申请号:SU802891750
申请日:1980-03-06
公开日:1987-06-23
发明作者:Греко Альберто；Бертолини Гулиельмо
申请人:Аник С.П.А (Фирма)；Снампрогетти С.П.А (Фирма)；
IPC主号:

专利说明:

The invention relates to methods for producing mixed metal alcoholates, which, after further chlorination, can be used as catalysts for the polymerization of olefins.
The purpose of the invention is to increase the activity of polymerization catalysts of α-olefins, which make it possible to obtain polymers with improved physicochemical characteristics with a higher yield by reducing the transition metal alcohol of the formula
M (OR) or VO (OR) j,
where M is Ti or Zr and R is a lower apical with metal vapors selected from the group Mg, Ca or A1, if necessary in the presence of aluminum alkoxide, in kerosene at a temperature from -20 ° C to room temperature and a pressure of 10 mm Hg. Art. with a molar ratio of the transition metal alcoholate to Mg, Ca or A1 equal to 0.46-26.6si, followed by keeping the reaction mass at 65-140 ° C and atmospheric pressure for 1-6 hours,
Examples 1-6. Restoration of titanium butylate (4.) in pairs of magnesium.
A rotating flask is used, in the center of which a Tungsten Table is located. 1 gives the conditions under which Ti (0-n-butsh1) 4 reduced - All metallic magnesium. Green or gray-green powdered | Solid products are filtered from. green kerosene, and then successively washed with n-heptane and dried under vacuum to analytically determine titanium and magnesium.
20 Analytical analysis is also carried out on filtered solutions.
E |) the evaporation efficiency of magnesium (molar ratio of evaporated magnesium / sum of magnesium in solution and solid magnesium / to magnesium, which was at the source) is 50-70% due to metal loss on the rods supporting the furnace, or on other auxiliary parts of the h.reactor. From 3Q, titanium / magnesium wearing varies depending on the reaction conditions between 2.3 (example 1, almost completely corresponding to pure mixed alcohol) and 8.0 (example 3, corresponding thread attached to a source of relatively pure Ti (35)). 0-electric power supply. A cooling bath is placed under the horizontally arranged flask. In the upper part of the apparatus there is an inlet for nitrogen and a device for evacuation.
Inside the spiral tungsten filament there is a wire of pure magnesium (the quantity is shown in Table 1) together with 250 ml of kerosene containing 2%, Ti (O-n-butyl). 250 ml of anhydrous kerosene containing Ti (O-n-butyl) c (the amount is shown in Table 1) is loaded into the flask under a nitrogen atmosphere.
-but w)). These facts confirm that due to the good evaporation efficiency of excess Ti (O-n-butyl) -, which does not undergo reaction, and
Q participates with Ti (O-n-butyl) in the separation of Mg (0 P-butyl), 2, giving a mixed alcohol Mg Ti (O-p-butyl), this product is soluble in hydrocarbons and this is the reason for the constant detection of magnesium in the mother liquor. When the reaction is carried out stoichiometrically i. to avoid any excess Ti (OR), magnesium precipitates along with the reduced
The rotating flask is cooled with 50 titanium alcoholate and neither titanium nor
using a bath up to -40 ° C, and then using a diffusion pump, pump out the contents of the flask to a pressure of 0.0001 mm Hg.
After these conditions are reached, the tungsten wire is heated until the metal is completely evaporated.
The metal evaporated in this way interacts with Ti (0-n-butyl 4 -Jt magnesium is not detected analytically in this way in mother liquors (Example 6),
All products are to a large extent amorphous according to X-ray emission and weakly paramagnetic.
Examples 7-11. Reduction of titanium alkoxides (44.) with magnesium vapor.
the result is a green (or gray-green) precipitate.
After the metal evaporates, vacuuming is stopped and the inner part of the flask is maintained at atmospheric pressure and room temperature by introducing nitrogen, after which the suspension is heated at 65-140 ° C for 1--6 hours.
Tab. 1 gives the conditions under which Ti (0-n-butsh1) 4 reduced - All metallic magnesium. Green or gray-green powdered | Solid products are filtered from. green kerosene, and then successively washed with n-heptane and dried under vacuum to analytically determine titanium and magnesium.
Analytical analysis is also carried out on filtered solutions.
E |) the evaporation efficiency of magnesium (molar ratio of evaporated magnesium / sum of magnesium in solution and solid magnesium / to magnesium, which was at the source) is 50-70% due to loss of metal on the rods supporting the furnace or other auxiliary parts of the h.reactor. The titanium / magnesium ratio varies depending on the reaction conditions between 2.3 (example 1, almost completely corresponding to pure mixed alcohol) and 8.0 (example 3, corresponding to Y relative to pure Ti (0-n-butr)) ). These facts confirm that, due to the good evaporation efficiency, an excess of Ti (O-n-butyl) -, which does not undergo reaction, and
participates with Ti (O-n-butyl) in the separation of Mg (0 P-butyl), 2, giving a mixed alcohol Mg Ti (O-p-butyl), this product is soluble in hydrocarbons and this is the reason for the constant detection of magnesium in the mother liquor. When the reaction is carried out stoichiometrically i. to avoid any excess Ti (OR), magnesium precipitates along with the reduced
titanium alcohol and neither titanium nor
magnesium is not detected analytically in mother liquors (Example 6),
All products are largely amorphous according to x-ray analysis and weakly paramagnetic.
Examples 7-11. Reduction of titanium alkoxides (44.) with magnesium vapor.
In tab. 2 shows the conditions of reduction for other titanium alkoxides other than Ti (O-n-butyl), as well as the yields and characteristics of the products obtained.
The suspensions obtained in the reduction reactions are green or gray-green with the exception of a suspension of Ti (OH-propyl), which is blue. When these suspensions are heated, the titanium / magnesium ratio in the precipitation changes completely (examples 9 and 10) as opposed to what is observed when Ti (O-n-butyl) is reduced. This effect is due to the greater solubility of Ti (0-i -propyl) J than Ti (0-n-butyl).
Examples 12-14. Reduction of Ti (O-n-butyl) with calcium or aluminum vapor.
The products are green, poorly soluble and are separated after treatments using methods similar to those in the previous examples. The data in examples 12-14 are presented in table 3
Example 15. Recovery of VO (O-i-propyl)} with magnesium.

Under the conditions of the experiment of examples 1-14, magnesium (47 mmol) is evaporated in a kerosene solution of VO (0-i-propyl) (100 mmol). After evaporation of the magnesium, the suspension is stirred for 2 hours at room temperature, the product is filtered and dried under vacuum (12 g, purple).
The product has the following composition,%: vanadium 17.9; magnesium 7.6. The vanadium / magnesium ratio is 1.1, and the evaporation efficiency is 75%.
Example 16. Reduction of Zr (0-n-propyl) 4 with magnesium.
Under the conditions of Examples 1-14, magnesium (40 mmol) is evaporated in a kerosene Zr (O-n-propyl) solution (50 mmol). The resulting gas is separated during evaporation. The contents are cooled at room temperature with vigorous stirring and after 4 hours the solid product is filtered off, repeatedly washed with kerosene and dried under vacuum (the yield is 1.2 g of gray pyrophoric powdered product).
The product has the following composition,%: zirconium 26.3, magnesium 1.8.
Example 17. Reduction of Ti (O-n-butyl) with magnesium in the presence of A1 (0-sec-butyl) ,.
Magnesium (35 mmol) is evaporated as per sample 1-14 in a kerosene solution of Ti (O-n-butyl) (80 mmol) and A1 (0- - sec-butyl) (18 mmol).
After evaporation, the mixture is cooled to room temperature with vigorous stirring for 1.5 hours, and then final heating for 2 hours at 105 ° C.
Green powder (9.6 g) is filtered off, washed with heptane and dried under vacuum. The product has the following composition,%: titanium 14.7J-magnesium 1.94, aluminum 0.66.
The filtrate contains 38 mmol of titanium, 15 mmol of magnesium and 13 mmol of aluminum. The evaporation efficiency is 65%.
Mixed metal alkoxides obtained in examples 1-17 can be used as intermediates for synthesizing an olefin polymerization catalyst.
The results of the polymerization of ethylene using a known catalyst and the proposed catalyst obtained from mixed alcoholic metals during their chlorination are presented in Table. four.
As follows from the table. 4, the chlorination of mixed metal alkoxides leads to the synthesis of a more highly active catalyst for the polymerization of olefins, which makes it possible to obtain polymers with improved physicochemical characteristics (with a narrower molecular weight distribution, good morphology: a lower content of very fine powder, more fluid, with a higher apparent viscosity) and with a high yield (with equal Mg / Ti ratios in new and known catalysts).

权利要求:
Claims (1)
[1]
Invention Formula
The method of obtaining mixed metal alkoxides for the catalyst for the polymerization of olefins, is made in such a way that, in order to increase the activity of the catalyst, a transition metal alcohol of the formula
M (OR) or VO (OR) 3,
where M is Ti or Zr R is lower alkyl.
interact with vapors of a metal selected from the group of Mg, Ca or A1., if necessary in the presence of an aluminum alkoxide, in kerosene at a temperature from -20 ° C to room temperature and pressure
80
33 65
Nezna- nezho- - nichitelno
Ispareine Hg is carried out at -20 ° C; evaporation time 30 min; kerosene solvent (fraction 200-240 ° C), 150 nl. The product is pyrophoric, has a molecular weight of 364.2, the data of the analysis are given in the grids. The product has a molecular weight of 704.1, the analysis data are shown in parentheses.
table 2
Alcohol Ti (OR),
AND,
7Ti (OEt), 80 35 703
1403
8ri (0-H-.
propyl), 80 35 1403
9Ti (0-i-progos 80 35 206
23 12 1.9 19.92 1.76 5.7 9.8 55
27 13 2.1 18.68 0.99 9.6 9.7 49 15 4 3, V 15.0 5.2 1.5 6.3 50
-four
 mm Hg, with a molar ratio of the alcohol of the transition metal to Mg, Ca or A1, equal to 0.46-26.6: 1, followed by holding the reaction mass at b3-HO C and atmospheric pressure for 1- 6 hours
t a, b l and d a
ten
eleven
12
13
14.9
3.25
2.3
6.5 Slightly
to - 80 35 140 336 .t, 9 196.20 15.04.33.8
(1 (0-H-.
-butyl), g
(OEt,) “O 30 BUT 318 27 0.87 8.21 8.50 0.5 3.0 Hee ah galna
Note. Evaporation is carried out under the conditions of Table. one.
Example
Alcohol t
 Ti (0-H-40-butylX
Sa
J3
, ()
20
A1
(k) .- The product has a molecular weight of 720, analysis data are in brackets. (and ") - The product has a molecular weight of 1047, the analysis data are given in brackets.
20.031 375 2500.4343.2
80,035 385 227,0,3952,9
1319782
8. Continuation of table 2
80
TlSq
Table 4
3.6 5
 0.044 540 420 0.39 A
 X. ; - V
13 0.026 155 125 0.40 4
Famous
0.114 400
88
Editor P.Geershi
Compiled by N.Kapitanova
Tehred L. Oliynyk Proofreader A.Zimokosov
2537/59
Circulation 371 Subscription
VNIIPY USSR State Committee
for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab, 4/5
Production and printing company, Uzhgorod, st. Project, 4
BUT
four
No shift
2.9
1.6
3.1
3.6
3. 32.4

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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IT20798/79A|IT1113421B|1979-03-07|1979-03-07|METHOD FOR THE REDUCTION OF METALLIC ALCOXIDS AND USE OF THE COMPOUNDS SO OBTAINED|

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