JPS58183704A - Olefin polymerization catalyst - 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 TECHNICAL DIVISION OF THE INVENTION The present invention is directed to novel catalyst compositions. More particularly, the present invention relates to a catalyst composition using a support containing magnesium, chlorine and bromine obtained by reacting an organomagnesium compound with a mixture of chlorinated and brominated aluminum compounds.

Description of advanced technology In this AIP, it is well known that a gold catalyst is used to polymerize olefins, such as 1,000 sulfur, propylene, 1-butene, etc., to produce high-molecular polymers. . This cypress gold-catalyst is of the Ziegler-Natsuta J type.
It is a stereoisomatic method of polymerizing reflexes resulting in the production of olefin polymers that are patented due to their high degree of isotacticity and crystallinity.

U.S. Pat. No. 4,104,198 to May Jr. et al. discloses treating a solution containing ethylaluminum sesquichloro-n-decylaluminum to produce a catalyst and using the catalyst to polymerize ethylene. is disclosed.

U.S. Pat. No. 4,168,881 by Jietzsell, however, combines an organomagnesium compound and a metal halide, such as aluminum trihalide,
Produce an intermediate reaction product that is subdivided, and then polymerize this intermediate reaction product and a titanium compound to form an olefin undercarriage catalyst! 41 is disclosed. Luciani et al., hJ Special*t82a 48143, describes (~ organometallic aluminum diamic compounds lacking a halide directly bonded to aluminum, Tol electron donating compounds, and (0) no\ halogen magnesium compounds). It has been disclosed that an olefin polymerization catalyst can be prepared by reacting solid compounds, which are reaction products, with a tetravalent titanium compound and an electron donating compound, and (2).

The novel catalyst composition of the invention comprises: 1. vitrocarbyl aluminum and CBltjiIJL treated with an AJ11 child donor compound and magnesium, the molar ratio of bromine to chlorine being from about 1=99 to about 50: 50, preferably about 2.6:97.5 to about 20:8
0, I & suitable about 2.5 F 97.5 to about 15 = 85
A support obtained by the reaction of an organomagnesium compound with a mixture of +4A-compounded and brominated aluminum compounds, the reaction product of the support being further treated with a child donor compound and titanium tetrachloride. I found that it consists of The molar ratio of magneum to chlorine and bromine combined in the support is not critical, but is generally from about 1:1.6 to about 12.0, and about 1:1. 1.8 to about 1 F 2.0 is preferred.

When the catalyst of the present invention is used in polymers of olefins as described above, high yields and high degrees of isotacticity are obtained in the polymer product.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The catalyst compositions of the present invention are prepared by reacting the organomagnesium compound with a mixture of tnw and brominated aluminum compounds. "Organomagnesium compound" candy shall be meant to include a divalent hydrocarbyl magnesium compound, the hydrocarpyl S content of which can be saturated or unsaturated, iI
The chain or branch alkyl chain has about 1 to about 24 carbon atoms, preferably about 1 to about 24 carbon atoms.

The gamma reel plate has from about 611 to about 20 carbon atoms, preferably from about 6 to about l[theta] carbon atoms. The alkenyl has about 6 to about 80 carbon atoms, preferably about 1 to 80 carbon atoms.
It has about 20 carbon atoms. The cycloalkyl slope has about δ to about 40 carbon atoms, tIr! L, < has about 81i to about 80 carbon atoms.

Aralkil chicks and Alkaril chicks have about 6 to about 40 IV1
1 carbon III atom, preferably about 6 to about 80 carbon III atoms. The magnesium compound is defined by the following formula.

MgR”, (MlR,).

(where n has 0 or more than 0, preferably O-4, and R1 and R1 can each be a hydrocarpylic slope as defined above.) Specific examples of organomagnesium compounds include: Includes: Diethylmagnesium, di-n-propylmagnesium, di-iso-propylmagnesium, di-n-butylmagnesium, di-sea magnesium, di-iso-butylmagnesium, di-hexylmagnesium, ethylbutylmagnesium, n-butyl -6eC-Butylmagnesium, diphenylmagnesium, dibenzylmagnesium, ditolylmagnesium, dicyclohexylmagnesium, magnesium aluminum pentaethyl, magnesium dialumium octaethyl, magnesium aluminum diethyl triisobutyl, magnesium aluminum dibutyl hexaethyl, magnesium Aluminum diphenylhexaethyl, magnesium aluminum dibutyl hexaethyl, magnesium sialuminum dicyclohexyl hexaethyl, magnesium sialuminum diethyl hexaethyl, etc. Among these, the following organomagnesium compounds are preferred. Diethylmagnesium, dibutylmagnesiums, maghondialium octaethyl, magnesium aluminum pentaethyl, magnesium sialumium diethylhex-isobutyl, and magnesium sialumium diisobutylhexaethyl.

# that can react with the above organomagnesium compounds
i-Nated and brominated aluminum compound iJ is represented by the following formula.

mj(R"R'R"'(11-al x&(R' in the formula
, R' and R6 are each hydrocarpylic as described above, X is chlorine or chlorine, and a is 1
It is an integer of ~8. ) Specific examples of chlorinated and brominated al-1-um compounds that can be used include the following: Aluminum tri-chloride, aluminum ethyl dichloride, aluminum diethyl monochloride, aluminum isobutyl dichloride, aluminum diisobutyl monochloride, aluminum diphenyl monochloride, aluminum dibenzyl monochloride, ethyl aluminum sesquichloride, aluminum n-butyl dichloride, aluminum di-n- Butyl monochloride, aluminum sea-butyl dichloride, aluminized-8ec-butyl monochloride, alkaline dialobyl dichloride, aluminum dialobyl monochloride, etc., and the corresponding bromides. Among these, the following chlorinated and brominated aluminum compounds are preferred. aluminum ethyl dichloride, aluminum ethyl dichloride,
Ethyl aluminum sesquichloride, aluminum dibutyl monochloride, aluminum butyl dichloride, etc.
and the corresponding bromide, and aluminum tribromide.

In the reaction of organomagnesium compounds with chlorinated and brominated aluminum compounds, these molar ratios can vary widely while the molar ratio of chlorine to bromine in the final carrier remains within the previously defined range. . For example, magnesium, chlorine and bromine in a ratio of about 1.0:1.0, respectively.
: 0.02-W is used in a molar range of approximately 1.0:10.0:5.0.

It is desirable to proceed with the reaction in the presence of an inert liquid diluent, preferably a hydrocarbon diluent such as benzene, toluene, cyclohexane, heptane. The amount of diluent used can vary over a wide range, but is generally between about 70 and 70 ml per total weight of the resulting slurry.
It contains about 99 quintillion percent, preferably about 90 to about 98 percent, diluent.

The reaction is carried out by stirring the slurry to open the fibers, and the temperature range is about -20° to about 180°C, preferably about 250 to about 1
10°C 1 minute to about 24 hours, preferably about 1 to about 8
Maintain a suitable inert atmosphere for a period of time, such as j:J'ff1l. Similarly, pressure is not critical, ambient pressure is preferred, but as low as about 25 mH9 or as high as 10-Op8ig (690kPa, '7~/cm''
) or higher pressures can be used if desired.

The reaction mixture is then maintained at ambient temperature and pressure and filtered. The recovered solids are then washed with a suitable hydrocarbon solvent such as those described above at ambient conditions or for about 2 hours.
The solids are then washed at temperatures ranging from 5' to about 100"C until the bulk hydrocarbon dissolved components are removed therefrom. The solids are then dried to remove any remaining hydrocarbons. This is all done in a suitable inert atmosphere. conduct.

The solid thus obtained contains substantially chlorine, bromine and magnesium suitable for use as a catalyst support.
There is.

The above reaction can be explained by the following equation.

(1) M 9R'g 10XA I R'Ol +
I 2-
Br(i-X)"2A/R'R'R' 1+g-X
) (2) MgR's+XAIR' C14, A'B
r5-111111stepM, l07xBr(2-x)+
, A4R'sR' + """A4R', 1(
2-X) (8) M, 7R', ・(AIR'81n+XA/
R'', Ol+-'T-mu1Br8-→1 11
+lX) '&"XBr(2-X)" 3m/R/, R' +
8 MulR', +nAIR'8 or (4) MAR', ・(A4R', ln+XAl',
(3j+(Ia-X)Mut R"zB r→M&"XB
r(2-Xl"2Aj!R' RI R"+nAJR
”.

(where R' t R' t and R71 are each a hydrocarbyl region as shown above, and X is about 1.0
~ about 1.98, preferably about 1.6 to about 1.95, sapon-
from about 1.7 to about 1.95, with n as indicated above).

In this reaction, the aluminum compounds are filtered 7 to remove them from the process forces, and after filtration the solid residue is washed using carbonization 7. The hydrocarbyl 7'luminium prepared in conjunction with the magnesium l\logenide support can be recovered and used to process the support for subsequent olefin polymerization as described above. Recovery of the desired hydrocarbyl aluminum can be accomplished by conventional methods;
For example, at a temperature of about 50' to about 150°C, about Q5
The filtrate is distilled to remove the solvent therefrom at a pressure of sa Hg to about 7601111 Hg.

The magnesium/X fluoride support thus obtained has a molecular weight of about 80 to about Is Om''/9, generally about 1
The support is then treated with a suitable electron donor compound (or Lewis-type compound). Examples of electron donor compounds that can be used include amines, amides, Ether, ketone, nitrile, phosphine, stilbene, arsine, phosphoramide, thioether, aldehyde, alcoholate, among the elements of the periodic table, there are the metals and the metals of groups 1 to 2 of the periodic table. Suitable acids are aromatic acids, such as benzoic a!
or p-hydroxybenzoic acid. Some examples of representative electron donor compounds include triethylamine, N
, N'-dimethylpiperazine, diethyl ether, n-
Includes dibutyl ether, tetrahydro-7rane, acetone, acetophenone, benzonitrile, tetramethylurea, nitrobenzene, Li-butyrate, dimethylaminophenyl lithium and Ha-dimethylamide. Preferred electron donor compounds include organic and inorganic oxygen-containing esters and ethers, such as n-dibutyl ether. Some suitable esters are) alkyl esters of 11[9, such as amine, iim, p-methoxy or p
- Ethoxyamine, l! Froic acid and p-tolylic acid, such as ammonium, ethyl hexazoate, p-methoxyammon, hexaethyl ethyl, p-
Methyl toluate and ethyl p-butoxybenzoate. Further examples of suitable esters include diethyl carbonate, triethyl borate, ethyl pivalate, ethyl naphtho-110-chlorobenzoate, ethyl acetate, dimethyl maleate, alkyl or aryl esters, and methyl methacrylate. Treatment with an electron donor compound can be carried out, for example, in the electron donor compound alone or in the presence of an inert liquid hydrocarbon carrier as indicated above, such as a magnesium bromine chloride carrier! The carrier may comprise, for example, from about 10% to about 50% of the resulting slurry. This slurry
As described above, under an inert atmosphere for a period of time from about 10 minutes to about 6 hours, or more, preferably from about 0.5 to about 4 hours, preferably from about 250 to about 150°C, <
i; j Warm stirring at about 50 DEG to about 100 DEG C., after which the slurry is made up to 11 Jl and the recovered solids are dried under vacuum. The dried solids are then mixed with titanium tetrachloride and the mixture is heated, for example, from about 10 minutes to about 6 hours, preferably about 0.
The mixture may be heated for 5 to about 4 hours at a temperature of about 50° to about 150°C, preferably from 80° to about 110"C.The served mixture is then filtered, preferably at a temperature of about 80"C. The recovered solids are then washed with a hydrocarbon solvent as described above to remove 1 g of dissolved hydrocarbons. The amount of titanium tetrachloride used is about 0.8% to about 811%, preferably about 0.8%, calculated as elemental titanium.
The amount yields a recovered solid product containing 7 to about 2.0 weight percent titanium. All this is done in a small active atmosphere as described above.

Magnesium bromine chloride treated with an electron donor compound and titanium tetrachloride is treated with hydrocarbyl aluminum treated with an electron donor compound.

Vitrocarbyl aluminum is defined by the following formula.

AIR'R7R8 in which Re, R7 and R8 are each a hydrocarpylic group as described above. Particularly preferred for this type of use are triethylaluminum, tolyl n-propylaluminum, triisopropylaluminum, tributylaluminum and triisobutylaluminum. Hydrocarbyl aluminum prepared in conjunction with a magnesium halide support, as described above, may be used in this step. Prior to use in the polymerization catalyst, the hydrocarbyl aluminum is contacted with an electron donor compound, such as those described above. The molar ratio of hydrocarbyl aluminum to electron donor compound is, for example, about 0.1:1.
~about 10:1, preferably about 0.5:1 to about 4
:1. In the treatment of the magnesium bromine chloride support and the electron donor compound, the conditions outlined above can be followed. Then <[1-L] the hydrocarbyl aluminum is added to the hydrocarbyl aluminum to titanium compound solubility ratio JO, 1:1 to about 1O:
1, preferably about 0.5:1 to about 4=1. Make it 5. Kosai1 is carrier wIfri2
! It is carried out at the same time. This support was treated with an electron donor compound and titanium tetrachloride as described above in a solution containing hydrocarbyl aluminum and an electron donor compound.

The resulting catalyst composition is combined with an alpha olefin, preferably at least 8 I return st atoms and optimal i: 4*
Alpha olefins having 5 atoms from 81 m to 10111 il can be used for polymerization. Examples include propylene, l-butene, 4-methyl-1-pentene, l-
Contains hexene, ■-octene, l-decene, etc. Copolymers of this cypress alpha olefin with each other or with ethylene can be obtained. The alpha olefin and catalyst are combined with each other in a polymerization reactor from about 85° to about 150° C1, preferably at a temperature of about 10° to about 80°C for about 5 hours, preferably about 1 to about 8 hours,
Ambient pressure to approximately 1 200 pBi & (8274k
Pa, 8 4.4 IC97 cm'), preferably (about 40 to about ao o psig (276 to 41
37 kPa, L8~42.2 kg7cm”)
(7) React using pressure. The catalyst is prepared in a non-reactive hydrocarbon solvent such as pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, toluene,
It is preferable to carry out MAI using xylene or the like.

At the end of the heating process, the pressure was released and the reaction product was reduced to 11J.
m, washed with a solvent, e.g. isopropanol, and Ll'
The IT polymer was collected and then dried. The isotactic degree of the polymer obtained from the above-mentioned enrichment process (5190
%, generally from about 97% to about 99% US. The yield of the chassis using the above catalyst is about 5% per 1g of titanium in the catalyst.
s, o009, generally from about 65,000 to about 200,000 s, or more, per gram of titanium. The diameter of the polymer particles is such that substantially all (more than 99%) have a particle size of more than 90μ. ing.

The invention will now be described by way of example.

EXAMPLE l In a three-tubular flask equipped with a stirrer, addition funnel, and reflux condenser, 500 - of anhydrous n-hebutane (20.1
Inject a self-prepared solution by dissolving 8 mol of M9. The reaction mixture was stirred while the temperature was raised to the boiling point of the solvent. After 6 hours, the flask was cooled to room temperature and the precipitate was added to solution A with stirring. Precipitate C was collected by filtration, washed with anhydrous n-hebutane, and dried under vacuum. 7 g of unbathable precipitate C was collected, which had a table tii[ of 15 om/9; g strip, g weight i 1% magnesium, 0.6 wt % aluminum and 65.
It contained 80% chlorine.

Precipitate C(1,19) was suspended in a f6 solution consisting of 4 g Lt of anhydrous 1-heptane and 11 ammonium, @ethyl froate, and the suspension was heated to 70 °C with stirring, for 4 hours. The song was held at this temperature. The mixture was filtered and the solid 10- recovered was washed with n-hebutane and dried. 10 to solid
- The temperature of the mixture obtained by adding Tic14 is raised to the boiling point (approximately 140° C.) while stirring. 8
After an hour, the humidity was lowered to 100°C, and the excess Ti0j
was filtered from the mixture and the recovered inert material was
It was washed twice with anhydrous n-hebutane and dried under a Jk hollow.

Whole word tN? l'&D (1,279)klj 18.9
fI amount 17)? It contained 0.65% aluminum, 1.4% titanium, and 58.8% #i by weight.

+ bath properties Df0.19) with 500 l/m of anhydrous n-hebutane, 0.6 yd of ml (G, H,)8 and 0
．． Ili! in a solution containing 84 ethyl anisate. Made it muddy. N, transfer the suspension to a l/l autoclave under vacuum,
The temperature was kept at 0°C. Propylene is then fed into the reactor while 901)8i (6211kPa, Li2
The contents were stirred until a pressure of kq/Cm") was reached. This pressure was maintained for 1 hour, then the propylene supply was stopped, the crepe was cooled in a room I!, and unreacted propylene was discharged. The contents of the autoclave were poured into 21 liters of isopropanol, filtered and dried.
g of isotactic polypropylene was recovered. The undercarriage slurry yielded 32.1489 propylene-enriched units per 12 titanium in the catalyst. It was found that 96% of the polymer was insoluble in boiling n-hebutane. What is the intrinsic viscosity [n] (in tetralin, 185°C)? 1.9
It was dl/9. All warpages are under nitrogen, except for polymer recovery? I built it.

Example 2 0,04 dissolved in 200 g Lt of anhydrous 1-heptane
Molten aluminum Aj, (C,H,), (0,H,l) in moles, dissolved in 70 ml of anhydrous n-heptane.
, 1 B moles of Al(C,H,l,Gl) and precipitate C were heated to boiling point temperature (approximately 9
TiC! The method of Example 1 was followed, except that it was not washed but dried under vacuum before treatment with .

Starting from 19 precipitates C, 0.95 g of insoluble *D were recovered. This material contains 20.8 iris of magnesium, 0.86% of aluminum by weight, 1.0 weight of 1I1
It contained 1% titanium and 57% chlorine by weight.

The electrolyte yield of this run was 58 g, giving 58.0009 polypropylene per gram of titanium. The intrinsic viscosity of the polymer is 4 J dj per gram, and 95% is insoluble in boiling n-hebutane. 7(0,H,), C7 and 0.0
The same procedure as in Example 4 below was followed except that 0.005 moles of AJBr were included. 89 Precipitate C was collected. Insoluble material D (0,979) was assembled starting from precipitate C of 19. 62 g of polypropylene worked in the polymerization. The intrinsic viscosity of the polymer is 4.9 dl/g;
8% was insoluble in boiling n-hebutane.

I 4 0,0δ dissolved in 160@t n-hebutane
has 5 moles of M9Aj, (0,H,)8 and has a dissolved DB of 5
0,056 mol of Mut (
The same method as in Example 8 was used, except that the sample contained 0.00 g of Br, at and 0.00 g of Br. 8g of Precipitate C was collected. This precipitate contains g11% magnesium,
It contained 0.1 wt. 11% aluminum, 47.8 wt. 11% chlorine, and 18.1 wt. bromine. Insoluble material 'MtD+0.84 g) was recovered starting from 0.959 precipitate C. Insoluble matter tD is 20.7 mei1%
of magnesium, 0.05% by weight of aluminum, o,
8wt 1g 1% titanium, 9.7wt% bromine and 58
．． It included a double i1% vote. Polymer collection 11ij
It became 909. A polypropylene polymer of 112.500Q per gram of titanium was obtained. ■Viscosity tjδ, 7 dt
/9) and was insoluble in 97% boiling n-heptane.

Example 5 The same method as in Example was used except that solvent A contained 0.08 moles of Mp(C,He)g instead of A/, (0,H,)8. A 13.189% precipitate was recovered containing 20% by weight magnesium, 0.4% aluminum, 131% bromine and 51.7% chlorine. Insoluble substance D (0,969), 1
Obtained starting from Precipitate C of 9. This is 18.4 irises i1
% of magnesium, 0.1% of aluminum, 1.
It contained 5% by weight titanium and 56.4% by weight chlorine. 100g of polypropylene polymer was recovered. This resulted in 6 fl, 6 B 79 polymer per 12 titanium in the catalyst. The intrinsic viscosity of the polymer was 8.8 di/9 and 97% was insoluble in boiling n-heptane.

Example 6 Bath solution B contains 0.08 mol M9(04He)s, solution B contains 0.049 mol M1(OsH,), C1,0,
004 mol AJBr and 0.037 mol Aj (
The method of Example 4 was followed except that C,H,)8 was included. Precipitate 0 (8,79) was collected. Insoluble substance D [0,
98)) was obtained starting from 0.98 cm of precipitate C.

The amount of polypropylene obtained was 55 g. The intrinsic viscosity of the polymer was 4.4 dl/9 and 98% was insoluble in boiling n-hebutane.

Example 7 Town Aj with 0.08 mol of bath liquid, (0, H5), +C
4H,).

5, and 0.08% molten KI B (D Aj(
0, H, ), (J and 0.016 mol of tOsH,
The method of Example t was followed except that Br. 0 sediments
(4.2 g) was obtained.

Starting from 1 g of precipitate C, 0.749 insolubles''
The iMD was collected. This logo contains 18.6% magnesium, 12% aluminum, 1.6% titanium, 17.9% bromine and 44.8% by weight.
Contains chlorine. 459 polypropylene were recovered. This is go, o o per gram of titanium.

It became a polymer of C. The intrinsic viscosity of the polymer is 8.8 di/
9, and 95% was insoluble in boiling heptane.

Example 8 In this l/7+1, M9A with 0.045 mol of dissolved MA
! gto, H6) 8 and i@IWB is 60gLt
7) The method of Example 2 was followed except that 11(0,H,), Br was included. 4. Precipitate C of δ was collected. This ft
lL contained 88% magnesium, 0.86% sodium bicarbonate aluminum and 80.5% bromine by weight. Using 8Q Precipitate C, an insoluble mass of 1.79 was obtained. This is 12.6%*Sagi% magnesium, 0.1
wt% aluminum, 1.0 m% titanium, 58.
It contained 4% by weight of bromine and 11% by weight of chlorine. The yield of polymer was 45 g. 45.0007 polypropylene was obtained per gram of titanium. The intrinsic viscosity was 8 Odl/g and 89.0% of the polymer was insoluble in boiling n-hebutane.

1: The data are shown in Table 1.

In the Table L, those obtained using the support of Example 3 (6) include those obtained when chlorine is the only halogen in the support (Examples 1 and 2) or when bromine is the only halogen in the support. (Example 8) or when the molar ratio of bromine to chlorine is outside the critical proportion (Example 7).

It is clear from the following experiments that it is critical to obtain magnesium bromine chloride by reacting a magnesium compound with a mixture of aluminized and odorized aluminum compounds.

Example 9 Precipitate a<halogenated magnesium compound), K.
General method of Ziegler and E. Holzkamp (Munn
, Chum, 605 (1957) 98)
Therefore, 0.007 mol (0,989> M g(3
-s Br and 0.08 mol (], 109) Mg
Conventional methods were followed except that an intimate mixture containing O,H,C1 and Al[O,H,1, was obtained by disproportionation. The product obtained was washed with anhydrous n-hebutane and dried in vacuo. Starting from precipitate C of 19, the unbathable product 'kD of 19 was prepared fI4. Elemental analysis of the insoluble substances was as follows. 18.7wt II 1% magnesium, 0.05wt 1% aluminum, 1.111wt 1% titanium, 6.6wt% bromine and 58.9wt% 1m element. The molar ratio of bromine to #i was 6:95. The amount of polymer obtained was 15 g. This corresponded to 11.588 g of polypropylene per gram of titanium. The intrinsic viscosity of the polymer is 8.5 di/9, which is 87%
only was insoluble in hot n-hebutane.

Patent applicant: Gulf Research and Development Company

Claims (1)

[Claims] L CA1 *Hydrocarbyl aluminum treated with a child donor compound and (81 having chlorine, bromine and magnification sium of 3, with a molar ratio of bromine to chlorine of about 1:99 to about 50:ISO A support obtained by the reaction of a magnesium compound with a mixture of an aluminum compound and a brominated aluminum compound, and further includes a reaction product of an electron donor compound and a support treated with titanium tetrachloride, such as aeJ. 2. The composition according to claim 1, wherein the molar ratio of magnesium to chlorine and bromine in the demolition carrier is from about 1:1.6 to about 1:2.0. 8. The organomagnesium compound is a divalent hydrocarbylmagnesium compound, and the hydrocarbyl moiety is an alkyl group having from about 1 to about 241 carbon atoms, an aryl group having from about 6 to about 40 carbon atoms. , an alkenyl group having about 1 to about 80 carbon atoms, about 3
Claim 1 wherein the slope is selected from the group consisting of cycloalkyl chicks having from 5 to about 40 carbon atoms, and aralkyl bridges and alkaryl chicks having from about 6 to about 40 carbon atoms. Compositions as described. 4 The organic magnesium compound is diethylmagnesium, di-n-propylmagnesium, di-iso-propylmagnesium, di-n-butylmagnesium, di-5
eC-butylmagnesium, di-iso-butylmagnesium, di-hexylmagnesium, ethylbutylmagnesium, n-butyl-6eC-butylmagnesium, diphenylmagnesium, Shihenzilmagsium, di[
Magnesium dicyclohexyl, dicyclohexylmagsium, magnesium aluminum pentaethyl, magnesium aluminum pentaethyl, magnesium aluminum diethyl triisobutyl, magsium aluminum dibutyl hexaethyl, magnesium sialium diphenylhexaethyl, magsium dialuminum dibenzyl hexaethyl, magsium % sialumium dicyclohexyl hexaethyl and magnesium sialumium diethyl hexabutyl.
! Flll11! The composition according to item 8, wherein the #A hydrogenated and brominated aluminum compound has the following formula % formula % (wherein R8, R4 and RIs are each about 1!l)
i! if ~ alkyl having about 24 carbon atoms;
Aryl folds with about 6 to about 20 charcoal particles, about 1
an alkenyl group having from 80 to about 80 carbon atoms, about 89
From the group consisting of cycloalkyl groups having ~40 carbon atoms, and aralkyl and alkaryl groups having ~6~40 carbon atoms, n1X is a salt S or bromine, and a(Δ1 Special #! is an integer of ~3) F#4 The composition according to the desired range item 1. a Said chlorinated and brominated aluminum compound'? I
Aluminum trichloride, aluminum ethyl dichloride, aluminum diethyl monochloride, aluminum isobutyl dichloride, aluminum diphenyl monochloride, aluminum dibenzyl monochloride, ~ethylaluminum sesquichloride, aluminum n-butyl dichloride, aluminum di-n-butyl monochloride 6. The composition of claim 5, wherein the composition is selected from the group consisting of aluminum 86G-butyl dichloride, aluminated-5ec-butyl monochloride, aluminum propyl dichloride, aluminum dipropyl monochloride, and their corresponding bromides. The composition of claim 1, wherein the molar ratio of bromine to chlorine in said carrier is from about 2.5297.5 to about 20780. & mJ period carrier has a molar ratio of bromine to chlorine of about 2.5297
．． 5 to about 15:85. Q The molar ratio of bromine to chlorine in the AiJ support is approximately 2.5207. - 5 to about 20,780. 10 The molar ratio of bromine to chlorine in the carrier is about 2.519.
7.5 - A composition according to claim 2m which is about 15:85. IL The bromine to chlorine molar ratio of the support is about 2.519.
5. The composition of claim 4, wherein the ratio is from 7.5 to about 20:80. 12 The bromine pair of the carrier 11! The elemental molar ratio is approximately 2.5
Claim 1 which is from 207.5 to approximately 15:85
Compositions as described in Section. 1 & previous body bromine vs 1! The elemental molar ratio is approximately 2.5197
．． 7. The composition of claim 6, wherein the ratio is from 5 to about 20:80. ]4 The molar ratio of bromine to chlorine in the carrier is about 2.5197.
．． 5 to about 15:85! FF The composition according to claim 6. The molar ratio of magnesium to chlorine to bromine of the compounds combined to obtain the support is about 1.0:1.0:0.
2 to about 1.0:10.0:5.0. 1& The molar ratio of magnesium to chlorine to bromine of the compounds combined to obtain the support is approximately 1.0 = 1.0:
0.2 to about 1.0: 1G, 0: 5. Or a composition according to claim 2. 1? The molar ratio of the compounds combined to obtain the carrier is about 1.0:1.0.
+ 0.2% - approx. 1,0: l O,0: 5. Or
A composition according to claim 1. l & the molar ratio of magnesium to chlorine to bromine of the compounds combined to obtain the support is about 1.0 +1, Oj O
,l! 7. The composition of claim 6, wherein the composition is between about 1.0 + 10.0 + 6.0. 19. The composition according to item 1, wherein the compound is combined with an inert diluent to form a slurry when obtaining a 4iJ century body. 2.alpha. The composition of claim 2, wherein in obtaining the carrier, the compound is combined with an inert diluent to form a slurry. 2L The composition of claim 4, wherein the compound is combined with an inert diluent to form a slurry when obtaining the carrier. The range 6 of the special t1111 request to generate slurry in combination
Compositions as described in Section. sl & The composition of claim 19, wherein the slurry is maintained at a temperature of about -80° to about 18°C for about 1 to about 24 hours. C. The slurry is maintained at a temperature of about 25° to about 110°C. The Ni material according to claim 19, wherein the Ni material is maintained at a temperature of about -20° C. for about 1 to about 8 hours. ga The slurry is maintained at a temperature of about -20° SJ #l 180° C. for about 1 to about 24 hours. 21. The composition of claim 20, wherein the composition maintains the slurry at a temperature of about 25 DEG to about 110 DEG C. for about 1 to about 8 hours. The composition according to item 21, wherein the slurry is maintained in a wet state at about -20°C to about 180°C for about 1 to about 24 hours. The composition of claim 2111, wherein the composition is maintained at a temperature of 25° to about 110°C for about 1 to about 8 hours.29.
23. The composition of claim 22, wherein the composition is maintained at 1 M for about 1 to about 24 hours. 8α The composition of claim 2g, wherein the slurry is maintained at a mt of about S6° to about 110°C for about 1 to about 8 hours. 8L of the carrier, alone or in the presence of an inert liquid hydrocarbon carrier, for about 10 minutes to about 6 hours at about 26°C.
81. The composition of claim 1, wherein the composition is treated with said electron donor compound at a temperature of ˜150" C. 81L said carrier alone or in an inert liquid hydrocarbon carrier. In existence, about 0.5 to about 4:1..., about 5
11. The composition according to claim 1, wherein the composition is subjected to vA turbidity at a temperature of 0 DEG to about 100 DEG C. and treated with the electron donor compound. δ & said carrier, alone or in the presence of an inert liquid hydrocarbon carrier, for about 10 minutes to about 6 hours, about 26° to
3. The composition of claim 2, wherein said electron donor compound is used at a humidity of about 150<0>C. 84 The carrier, alone or in the presence of an inert liquid hydrocarbon carrier, is heated at about 50° for a ringing time of about 0.5 to about 50°.
to about 100° C. (7): a1 nitrate M is suspended and treated with the electron donor compound. Claim 8
Compositions as described in Section. 85 The carrier, alone or in the presence of an inert liquid hydrocarbon carrier, for about 10 minutes to about 6 hours, about 115'
5. The composition of claim 4, wherein the composition is treated with said electron donor compound by heating at a temperature of 150 DEG C. to about 150 DEG C. 1% of the electron donor, alone or in the presence of an inert liquid hydrocarbon bulk carrier, at a temperature of about 50° to about 100° C. for about 0.6 to about 4 hours. The compound according to claim 4, which is treated with the compound. 8) The carrier, alone or in the presence of an inert liquid hydrocarbon, for about 10 minutes to about 6 hours, about 26
7. The composition of claim 6, wherein the composition is treated with said electron donor compound by WIA at a temperature of about 150°C. 8 & said carrier, alone or in the presence of an inert liquid hydrocarbon carrier, for about 0.5 to about 4 hours, about 50' to
7. The composition of claim 6, wherein the composition is treated with said electron donor compound at a temperature of about 100<0>C. 89. The support is then mixed with titanium tetrachloride and heated at a temperature of about 50° to about 160° C. for about 10 minutes to about 6 hours, to give a concentration of about 0.000° C., calculated as elemental titanium.
81. The composition of claim 81, wherein a solid product containing from 8 to about 8 weight percent titanium is recovered. The 4α-Eleventh carrier was mixed with titanium tetrachloride and heated for about 0.5 to about 4 hours at a temperature of about 80° to about 140°C, and the material was mixed with titanium tetrachloride to give a MFm of about 100% titanium. 83. The composition of claim 82, wherein a solid product is recovered containing 0.7 to about 2.0 weight percent titanium. The frog AiJ period carrier is then mixed with titanium tetrachloride,
Heating at a humidity of about 50°C to 160°C for about 10 minutes to about 6 hours, and then about 0.8 to 160°C calculated as titanium element.
89. The composition of claim 88, wherein a solid product containing about 8% by weight of titanium is recovered. The carrier is then mixed with titanium tetrachloride and about 0%
．． Heating at a temperature of about 80° to about 140°C for 5 to about 4 hours, then about 0.7 (calculated as titanium element)
85. The composition of claim 84, wherein a solid product is recovered having about 2.0% titanium by weight. 4 & Said support is then mixed with titanium tetrachloride and heated at a temperature of about 50' to about 150° C. for about 10 minutes to about 6 o'clock, so that about 0.8 ~
86. The composition of claim 85, wherein a solid product is recovered containing about s ii% titanium. Mix the carrier with its whip, titanium tetrachloride, about 0
．． Heating at a temperature of about 80° to about 140″C for 5 to about 1 hour, then about 0.7 to about s calculated as elemental titanium.
87. The composition of claim 86, wherein a solid product containing 1% titanium in .ol is recovered. 45. The carrier is then mixed with titanium tetrachloride and heated in a wet environment at about 50° to about 150° C. for about 10 minutes to about 6 hours, and then heated to about 0.8 to about 0.8 to about 150° C., calculated as elemental titanium. 88. The product of claim 87, wherein a solid product having about 8 weight percent titanium is recovered. 4a the support is then mixed with titanium tetrachloride;
112 at about 80° to about 140°C for about 0.5 to about 4 hours
89. The product of claim 88, wherein the product is heated to 1° C. and then recovered as a solid product containing from about 0.7 to about 2.0% by weight titanium calculated as elemental titanium. 47, 6fJU hydrocarbyl aluminum to 1 ethyl aluminum, tri-n-propyl aluminum,
A composition according to claim 1 selected from the group consisting of tri-iso-propyl aluminum, tri-n-butyl aluminum and tri-iso-butyl aluminum. 3. The composition of claim 2, wherein the aluminum hydrocarbyl is selected from the group consisting of triethylaluminum, tri-n-propylaluminum, tri-iso-propylaluminum, tri-n-butylaluminum and tri-iso-butylaluminum. 49. The composition of claim 4, wherein said hydrocarbyl aluminum comprises triethylaluminum, tri-n-propyl aluminum, tri-isopropylaluminium, tri-n-butyl aluminum, and tri-iso-butyl aluminum. 5α ItiJ The composition according to claim 6, wherein the hydrocarbyl aluminum is selected from the group consisting of triethylaluminum, tri-n-propyl aluminum, tri-iso-propyl aluminum, tri-n-butyl aluminum and tri-iso-butyl aluminum. 61 The hydrocarbyl aluminilla b can be prepared by hand or in the presence of an inert liquid expanded hydrogen carrier at a concentration of about 1O
The composition of claim 1, wherein the composition is incubated with the electron donor compound in a humid environment at about 25 DEG to about 160 DEG C. for a period of minutes to about 6 hours. B! Said hydrocarbyl aluminum hwo, 11L1
The electron donor compound is suspended in JI or in the presence of an inert liquid hydrocarbon carrier for about 0.5 to about 4 hours at a temperature of about 500 to about 100°C.
A composition according to claim 1. 5&lIJ hydrocarbyl aluminum, alone or in the presence of an inert liquid hydrocarbon carrier, about 10
The composition of claim 2, wherein the composition of claim 2 is treated with the electron donor compound at a temperature of about 26° C. to about 150° C. for a period of about 6 hours. Alone or in the presence of an inert liquid hydrocarbon carrier, about 0. ! 1 to about 4 hours, about 50
9. The composition of claim 8, wherein said hydrocarbyl aluminum is suspended and treated with a predistributed electron donor compound at a temperature of from 100 °C to about 100"C. In the presence of a hydrocarbon carrier, about 1
3. The composition of claim 2, wherein said hydrocarbyl aluminum is suspended and treated with said electron donor compound at a temperature of about 15 DEG to about 11 SO" C for 0 minutes to about 6 hours. , single s”c
or with said electron donor compound suspended at a temperature of about 60° to about 1°C for about 0.5 to about 4 hours in the presence of an inert liquid hydrocarbon carrier. The composition of claim 2, wherein the composition of claim 2 and drocarbyl aluminum are treated alone or in the presence of an inert liquid hydrocarbon carrier for from about 10 minutes to about 6 hours, from about 26° to about 150°C. 0511L ME hydrocarbyl aluminum, alone or in the presence of an inert liquid hydrocarbon carrier; inside, about 0.5 to about 1 hour, about 60° to about 100"
At a temperature of C! 7. The composition of claim 6, wherein the composition is treated with said electron donor compound.