CA1069109A - Catalyst and a polymerization process employing the catalyst - Google Patents

Abstract

Abstract of the Disclosure Alpha olefins are polymerized employing a catalyst which forms on mixing a first component resulting from admixture of a halogenated titanium compound, a Lewis base and a magnesium or manganese halide; a second component which is an organoaluminum compound; a third component which is a Lewis base; and a fourth component which is an organoaluminum monohalide.

Description

106~109 Background The present invention relates to a catalyst, a method for making the catalyst and a polymerization process èmploying the catalyst.
In the field of catalytic polymerization of oléfins such as propylene to produce useful solid polymers, a continuing objective is to increase productivity. By productivity is meant the amount of useful solid polymer that is obtained by means of a given quantity of catalytic materials. This is important because the removal of catalytic materials from the solid polymer is almost always necessary and is generally troublesome or expensive to carry out. Thus, improved polymerization processes are desired in which the productivity of the polymer per unit of catalyst materials i8 SO great that the amount of catalyst residues remaining in the polymer is insignificant and the catalyst removal steps can be minimized or omitted.
~ne known catalyst system which is said to exhibit a relatively high productivity employs two components wherein the first component is prepared from materials such as titanium tetrachloride, ethyl benzoate, and magnesium chloride and the second component is prepared from materials such as triethylaluminum ant ethyl anisate. Such a catalyst system is said to produce large quantities of solid polymer per unit of catalyst.
It is known that an improvement in the type of catalyst repre-sented above is alleged by the incorporation of a solid organic material into the first component which is inert to the catalyst component. An example of such a material is durene. The incorporation of a material such as durene is said to improve the stereospecific nature of the catalyst and provide yet a higher yield of usable polymer per unit of catalyst.
The present invention provides still higher yields of usable polymer per unit of catalyst as compared to the above known catalysts.
Summary In accordance with the invention, a catalyst is provided which ~ ' .

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fo D on mixing a first component resulting from the admixture of (1) a halogenated bivalent, trivalent, or tetravalent titanium compound, (2) a Lewis base and (3) a compound selected from the group consisting of magnesium and manganese dihalide; a second component wherein said second component is a compound selected from the group consisting of a trialkyl-aluminum compound and an organoaluminum compound having 2 or more aluminum atoms bonded to one another by an oxygen or a nitrogen atom; a third component wherein said third component is a Lewi~ base; a fourth component wherein said fourth component is an organoaluminum monohalide represented by the general formula AlR2X wherein the R groups represent alkyl radicals having from 1 to about 12 carbon atoms, said R groups being the same or different, ant X represents a halogen atom.
Further, in accordance with the invention, alpha-olefins are polymer-lzed under polymerization conditions employing the above catalyst.
Further, in accordance with the invention, a catalyst is prepared by mixing a first component resulting from the admixture of (1) a halogenated bivalent, trivalent or tetravalent titanium compound, (2) a Lewis base and (3) a compound selected from the group consisting of magnesium and manganese di-halite; a second component selectet from the group consisting of a ~rialkyl-aluminum compound and an organoaluminum compound having 2 or re atoms bonded to one another by an oxygen or a nitrogen atom; a third component, said third component being a Lewis base; and a fourth component, said fourth component being an organoaluminum monohalide represented by the general formula AlR2X
wherein the R groups represent alkyl radicals having from 1 to about 12 carbon atoms, said R groups being the same or different, and X represents a halogen atom.
Detailet Description of the Invention A broat range of olefins can be polymerized by the process and catalyst system of the present invention. Commercial value can be visualized presently with alpha olefins which have from 2 to about 6 carbon atoms. The invention finds particular usefulness with either - ~ -3-~.

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ethylene or propylene which is polymerized to produce polyethylene or polypropylene, respectively. Mixtures of the alpha olefins can be used.
Very high ratios of polypropylene to catalyst were obtained employing the catalyst and process of the present invention.
The catalyst system of the present invention consists of several essential components. The first component comprises a halogenated bivalent, trivalent or tetravalent titanium compound, a Lewis base and either magnesium or manganese dihalide. These compounds are such that their mixture, when contacted with one or more other catalyst components, pro-duces a product active for olefin polymerization. Regarding the titanium compound, generally titanium tetrahalides are used. As an example, titanium tetrachloride has been used with very good results.
Lewis bases are used in the present invention, both in the first component of the catalyst and for the third component of the catalyst.
Suitable Lewis bases include organic compounds such as amines, amides, ethers, esters, ketones, nitriles, phosphines, etc. Particularly appli-cable are esters represented by the formula:
O
ll C - O - R' [~

R"
wherein R' represents alkyl groups having from 1 to about 4 carbon atoms and wherein R" represents monovalent radicals selected from the group consisting of -F, -Cl, -Br, -I, -OH, -OR', -OOCR', -SH, -NH2, -NR2, -NHCOR', NO2, -CN, -CHO, -COR', -COOR', -CONH2, CONR2, -SO2R', -CF3, and hydrogen. Some examples of such compounds are ethyl benzoate, ethyl anisate (p-methoxybenzoate), ethyl p-dimethylaminobenzoate, ethyl p-fluorobenzoate, ethyl p-cyanobenzoate, methyl benzoate, isopropyl p-.
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~069109;

diethylaminobenzoate, butyl p-fluorobenzoate, n-propyl p-cyanobenzoate, ethyl p-trifluoromethylbenzoate, methyl p-hydroxybenzoate, ethyl p-methoxycarbonylbenzoate, methyl p-acetylbenzoate, isopropyl p-formyl-benzoate, methyl p-nitrobenzoate, ethyl p-carbamoylbenzoate, methyl p-mercaptobenzoate and mixtures thereof. The Lewis bases uRed in the first component and for the third component of the catalyst can be the same or different; however, particularly good results were obtained employing ethyl benzoate in the first component and ethyl anisate for the third com-ponent. Similarly, good results were obtained using ethyl benzoate in both the first and third components.
Regarding magnesium dihalide and manganese dihalide, generally magnesium dihalide i8 used. As an example, very good results were obtained using magnesium dichloride.
The second component comprises a trialkylaluminum compound or an organoaluminum compound having two aluminum atoms bonded one to another by an oxygen or a nitrogen atom. Of the two types of organoaluminum com-pounds suitable for use in the second component of the catalyst, the tri-alkylaluminum compounds are generally used. Suitable trialkylaluminum compounds are those corresponding to the general formula AlR3 wherein R
represents alkyl groups having from 1 to about 12 carbon atoms. The R
groups can be the same or different. Some examples of these compounds are ~-triethylaluminum, trimethylaluminum, tri-n-propylaluminum, triisobutyl-aluminum, tri(2-ethylhexyl)aluminum, dimethylethylaluminum, tri-n-amylaluminum, tri-n-dodecylaluminum and mixtures thereof. Very good results were obtained employing triethylaluminum.
The organoaluminum compounds with two or more aluminum atoms bonded to one another by an oxygen or a nitrogen atom are usually obtained by the reaction of a trialkylaluminum compound with water, a~monia, or a primary amine in accordance with known processes. Among such suitable compounds are those represented by the following formulas~

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(C2H5)2Al-0-Al(C2H5)2 and (C2H5)2Al-N-Al(C2H5)2 The fourth component of the catalyst is an organoaluminum mono-halide. The organoaluminum monohalide compounds which are applicable for use in the present invention are those compounds represented by general formula AlR2X wherein R represents an alkyl group having from 1 to about 12 carbon atoms and wherein X represents a halogen atom. The R groups can be the same or different. The halogens most often used are chlorine and bromine and compounds containing a chloride atom are generally pre-ferred because very good results were obtained using them and they are readily available. Some examples of suitable organoaluminum monohalide compounds are diethylaluminum chloride, dimethylaluminum chloride, methyl-ethylaluminum chloride, diethylaluminum bromide, di-n prQpylaluminum chloride, ethyl-t-butylaluminum bromide, di-(2-ethylhexyl)aluminum chloride, diethylaluminum fluoride, di-n-butylaluminum chloride, dimethyl-aluminum iodide, di-n-dodecylaluminum chloride and mixtures thereof.
Very good results were obtained by employing a catalyst-improving solid organic material as a part of the first component of the catalyst, although it is pointed out that the invention is not limited in scope to the use of such materials. The solid organic materials appear to be inert with respect to the second, third and fourth components or compounds used in the invention, and as previously indicated, such materials are incor-porated into the first component of the catalyst during the preparation of the first component. Although the material is referred to as a solid organic material, as described below, the material is normally in a particulate or pulverized state after it is incorporated in the first component of the catalyst. These materials appear to improve the stero-specificity of the catalyst system and can be either relatively low ~Q69109 molecular weight compounds or they can be polymeric materials! Some examples are durene(2,3,5,6-tetramethylbenzene), anthracene, hexachloro-benzene, p-dichlorobenzene, naphthalene, polyvinyltoluene, polycarbonate, polyethylene, polypropylene, polystyrene, polymethylmethacrylate and mix-tures thereof. Durene was used in a number of runs and found to be particu-larly effective.
In the preparation of the first component of the catalyst the halogenated titanium compound, the magnesium dihalide or manganese di-halide, the Lewis base and solid organic material, if used, are blended or mixed in any suitable manner which will provide a finely divided solid material which, when suitably reduced, provides an active catalyst compo-nent of the invention. The reducing agent is usually a mixture of the second component and ~he third component of the catalyst system; however, the second and third components need not be mixed together prior to con-tacting the other components of the catalyst. Good results were obtained by combining the materials comprising the first component of the catalyst system in a ball-mill, but other grinding means or similar equipment can be used. Further, it is frequently helpful if the magnesium dihalide or manganese dihalide is subjected to a separate grinding operation before mixing it with the other materials making up the first catalyst component and subsequently grinding the mixture as earlier described.
The proportions of the halogenated titanium compound ~nd the Lewis base compound are presently not believed to be critical since it is believed that an equimolar complex is formed regardless of the relative amounts used; however, it is recommended that the ratio of titanium com-pound to Lewis base be in the range of from about 0.7:1 to about 1.3:1.
The first catalyst component will generally contain from about 35 to about 65 weight percent magnesium or manganese dihalide, from about 10 to about 60 weight percent solid organic material, if used, and from about S to about 25 weight percent of the halogenated titanium compound-Lewis base , ~ . , . , - ... .
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complex. If the solid organic material is not used then the first catalyst component will generally contain from about 50 to about 95 weight percent magnesium or manganese dihalide and from about 5 to about 50 weight percent of the halogenated titanium compound-Lewis base complex. The first catalyst component can be prepared at any suitable temperature and pressure, ambient temperature generally being used.
It has been found convenient to mix the second and third compo-nents together prior to contacting them with the other catalyst components;
however, it is understood that the second and third catalyst components can be contacted with the other catalyst components separately if desired.
The second catalyst component of the catalyst system comprises an organo-aluminum compound (trlalkylaluminum compound or the organodialuminum com-pound) and the third component comprises a Lewis base. The Lewis base can be the same or different from the Lewis base employed in the preparation of the earlier-described first catalyst component. The mixture is pre-pared by contacting the trialkylaluminum or organodialuminum compound with the Lewis base under any æuitable conditions of temperature. The contact can be carried out either in the presence or absence of a diluent but an inert hydrocarbon diluent such as hexane, heptane, and the like is convenient. The quantity of diluent i8 not critical.
The molar ratio of the organoaluminum compound of the second component to the Lewis base of the third component can be selected over a substantial range depending upon the specific compounds used. Generally, the aluminum compound to Lewis base molar ratio will be in the range of from about 1:1 to about 8:1. As an example, good results were obtained employing a molar ratio of triethylaluminum to ethyl anisate in the range of 1.5:1 to 6.0:1. Normally the mixture of the second and third components of the catalyst is in a liquid state.
If desired, the fourth component of the catalyst system, the AlR2X compound, can be incorporated into the mixture of the second and ----' 1069~09 third catalyst components by simply mixing, preferably in the presence of a convenient hydrocarbon diluent. Any order of contact can be used to contact the Lewis base, the organoaluminum compound, and the AlR2X com-pound. It is presently believed that a desirable complex is formed between the organoaluminum compound of the second catalyst component and the Lewis base of the third catalyst component. The incorporation of the AlR2X
compound into the liquid of the second and third catalyst components can be carried out at any convenient temperature, for example ambient tempera-ture or even at polymerization process temperature.
The conditions for the polymerization process will generally be similar to those well known for related processes using a reduced titanium catalyst system. The process is conveniently carried out in the liquid phase in the presence or absence of a diluent such as an inert hydrocarbon, e.g., n-heptane, isobutane, cyclohexane, etc.; however, it is understood that the invention is not limited to liquid phase reactions. If no diluent is used, then the reaction is carried out in liquid monomer. The polymerization te~perature can be selected from a range of temperatures -~depending upon the specific monomers employed and the mode of reaction, but it will generally be in the range of 60-212F (15.5-100C). As an example, the polymerization of propylene using a liquid propylene phase is conveniently carried out in the range of from about 75 to about 175F ;
(24-80C), although it is preferred to employ a temperature in the range of from about 120 to about 160F (49-71C) because of better results ~-with regard to productivity and solubles. The polymerization pressure can be any convenient pressure. When a liquid phase reaction is carried out, of course the pressure will be such as to maintain the reactants in the liquid phase within the reaction zone. Control of the molecular weight of the polymer by the presence of small amounts of hydrogen during poly-merization is a well known procedure and can be used to advantage in the present inventive process.

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The polymerization process can be carried out continuously or batchwise.
The proportions of the first catalyst component and the second catalyst component in the reaction zone will depend somewhat on the amount of catalyst poisons, such as water and air, etc., present during catalyst preparation and in the polymerization system. Since the second catalyst component, the organoaluminum compound, is the primary catalyst component attacked by such poisons, the amount of the second component required in the invention is that amount inactivated by the poisons plus the amount needed to obtain the increase in productivity. In essentially poison-free systems the molar ratio of the aluminum compound of the second component to the titanium compound of the first component can be as low as on a one-to-one basis. In systems with a high poison level the molar ratio can be several hundred times that of the poison-free system. Thus the lar ratio of the aluminum compound of the second component to tbe titanium compound of the first component can be selected from a wide range. Generally, a molar ratio in the range of from about 1:1 to about 150:1 is used; however, it is presently recommended that a molar ratio be selected in the range from about 25:1 to about 125:1. Regarting the molar ratio of the fourth ~ 20 component to the irst component, the amount of AlR2X compound introduced ; into the reaction zone can be selected from a broat range of ratios, but t it is recommended that the molar ratio be such as to provide a AlR2X to titanium molar ratio in the range from about 0.5:1 to about 200:1, usually 2:1 to about 150:1.
All the catalyst components can be individually introduced into the reaction zone or can be combined in various ways. Some of the pro-; cedures for introducing the catalyst materials into the reaction zone are:
charging the fourth component followed by a premixed slurry of the first, . . .
second and third catalyst components; charging the first component followed by the fourth component and nomer then followed by the second ..

~069109 component together with the third component flushed in with a liquid solvent or monomer; charging a mixture of the second, third and fourth components followed by liquid propylene and then the first component;
charging the first component followed by a portion of monomer and followed by a mixture of the second, third and fourth components flushed with additional monomer.
It has been found that if the catalyst components are mixed together employing a mixing temperature ranging from about -120F to about 80F (-84C to 27C), a higher yield of useful polymer is produced per unit of catalyst as compared to the amount of useful polymer produced -employing the same catalyst prepared at a mixing temperature of approxi-mately 150F (66C) and higher. Any order of mixing of the catalyst com-ponents can be used and still obtain the higher yield of useful polymer -~
if the recommended range of mixing temperatures is used. It is presently believed desirable not to contact the first component and the fourth com-ponent together at temperatures of about 150F (66C) or higher in the abæence of monomer or the second component.
After completion of the polymerization reaction or after a suit-able residence time in the reaction zone, the reactor contents are dis-charged, ~reated with an agent such as alcohol to inactivate the catalyst system, then the mixture is separated and the polymer isolated and purified~
by a suitable procedure such as by drying under vacuum.
Specific ExamPles Example I
The effect of the presence of diethylaluminum chloride (DEAC), a compound representative of the fourth component of the catalyst system, was demonstrated in a series of runs in which propylene was polymerized to a solid polymer in batch runs utilizing a catalyst system prepared from magnesium chloride (MgC12), titanium tetrachloride (TlC14), triethyl-aluminum (TEA), ethyl benzoate (EB), ethyl anisate (EA), and durene.

~069~09 The first component of the catalyst system was prepared by ball milling 5.0g MgC12, 5.0g durene, 2.7g of a 1:1 molar yellow complex of TiC14 and EB in a l-quart bottle filled with 550g of 3/8 inch SS balls.
The MgC12 had previously been ball-milled by itself and dried at 300C.
The mixture was ball milled for three days at room temperature then passed through a 100 mesh U.S. sieve series screen.
A mixture of the second component and the third component of the catalyst system was prepared by mixing 45 cc hexane, 0.44cc (0.48g) EA and 0.82g (7.4cc of hexane solution) of TEA.
In a run made without the fourth component a l-liter stirred autoclave was flushed with nitrogen then charged with 0.1297g of the above-prepared first catalyst component, and the above-described solution of the second and third catalyst components. The charging was carried out under a gaseous propylene flush. About 200g liquid propylene was then added together with l-liter (STP) of hydrogen. The reactor and contents were then heated to 140F (60C) and additional liquid propylene was added intermittently to maintain the reactor in a liquid full condition. After one hour, the reactor contents were discharged, washed with methanol and dried under vacuum.
In the same manner as in the above run, other runs were carried out except that small amounts of DEAC were added to the reactor prior to the addition of the first, second and third catalyst components.
The results of the above runs are shown in Table I.
The data in Table I show the unexpected benefits obtained by the ~ -presence of DEAC in the polymerization zone. Run 1 is a control run showing the results obtained in a DEAC-free system. In Run 2, a portion of the TEA in the second catalyst component was replaced with DEAC and resulted in a small change in productivity and an increase in xylene solubles. In Run 3 when the TEA was completely replaced by DEAC in the second catalyst component, the productivity fell drastically while the solubles ~umped again. Thus, there appeared to be little or nothing to gain by replacing some or all of the TEA by DEAC. - -In Run 4, however, when a small amount of DEAC was added to the reaction zone while maintaining the desired TEA/EA ratio, a very large increase in produc~ivity was unexpectedly obtained along with only a modest increase in solubles. The data indicate that the DEAC very likely functions in a manner at least partially different from the reducing function of the TEA.
Because the reactor was very full of polymer at the completion of the one hour run in Run 4, the total a unt of catalyst was reduced in invention Run~ 5 and 6 to provide opportunity for still greater produc-tivity and to improve temperature control.

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Example II -In another series of runs, propylene was polymerized both in the presence and absence of DEAC under conditions different from those of Example I. In these runs, ethylbenzoate (EB) was used to complex both the TiC14 and the TEA.
The first component of the catalyst system was prepared by milling lOg MgC12, 2.8g TiC14, 2.2g EB and lOg durene in a 250cc high energy mill t(Vibratom manufactured by Siebtechnik GMBH, 433 Mulheim (RUHR), Germany]
containing 200g of 3¦8 inch SS balls for a total of 73.5 hours. A mixture of the second and third catalyst components was prepared by mixing appropriate amounts of hexane solutions of TEA and EB.
A l-liter stirred autoclave, free of air or moisture, was charged with: the first component of the catalyst; a hexane solution of DEAC (when used); a 50cc hexane flush; the appropriate amounts of the mixture of the second and third components; about 0.5 liter of hydrogen measured at standard conditions (STP); and about 1/2 liter of liquid propylene. The reactor and contents were heated to 140P (60C) and additional liquid propylene was added intermittently to maintain a liquid-full condition. After one hour, the reactor contents were tischarget, washet with methanol and driet unter vacuum.
Table II shows the e~sential conditions and results of these runs.

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Polymerization of Propylene Xylene Run Molar Ratio Productivity Solubles No. TEA/EB TEA/Ti DEAC/Ti 8/8 TiWt. %
1 3 96 0 107,0007.4 2 3 96 96 129,000C10.2

3 3 96 96 207,000d10.7

4 3 96 42 172,00Oe8.9 3 96 42 163,00010.6 6 3 97 42 201,00016.6 7 3 95 42 147,000b14.4 8 3 96 42a 174,00013.9 Notes:
a. The DEAC was mixed with the TEA and EB before being introduced into the reactor. In all other runs, the DEAC preceded the TEA-EB mixture.
b. This run at 130F. All others at 140F.
c. Experienced overheating of reactor up to 175F.
d. Experienced brief fluctuation (130-147F).
e. Experienced 1088 of temperature control ~ 120-160F).

The data in Table II again show that the presence of DEAC in the polymerization system significantly increases the production of useful solid polypropylene with generally modest increases in the solubles.
Inventive Runs 2-8 also illustrate two additional modes of DEAC addition.
In one mode of addition the DEAC was introduced into the reaction zone immediately following the introduction of the first catalyst component, and in the other mode of addition the DEAC was pre-mixed with the TEA
and EB (second and third catalyst components) at room temperature prior to in~ection into the reaction zone as in Run 8.

1~69109 Example III
In another series of runs, propylene was polymerized using the -invention process under still different conditions including different modes of addition of catalyst components to the reaction zone. The first catalyst component was prepared in a manner similar to that des-cribed in Example II. The second and third catalyst components consisted of triethylaluminum (TEA) and ethyl anisate (EA), respectively. The runs were carried out in a one-gallon autoclave but otherwise in a manner similar to that of Example II. The reaction temperature in the one hour runs, was 150F (66C) and 900cc of hydrogen at STP were present in each run. The other essential conditions and results of these runs are shown in Table III.
The data in Table III still further illustrates the beneficial effects obtainable from the incorporation of DEAC in the polymerization zone. Also, different modes of contactlng the catalyst components are shown.
Speclfically, invention Run 2 can be compared with control Run l; invention Run 4 with control Run 3; invention Run 6 with control Run 5;
and invention Run 8 with control Run 7. In each instance, the presence of DEAC is seen to substantially increase the productivity, with little or no increase in undesirable solubles.
Run 10 compared with Run 9 illustrates the advantage of main- -taining a relatively low temperature when the first catalyst component is contacted with DEAC in the absence of the second and third catalyst compo-nents.

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o, o 1069~09 Notes~
a. This run at 140F. All others at 150F.
b. DEAC in this and subsequent runs when used is the fourth catalyst component.
c. C3= is used to denote liquid propylene.

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` f-`-`` 1069109 SUPPLEMENTARY DISCLOSURE
Detailed Description of the-Invention It has been found that a Lewis base is not essential in the first component of the catalyst of the present invention. The preparation of the catalyst is identical to that previously described but the Lewis base is `~
simply omitted from the preparation of the first component. Good results were obtained employing a Lewis base in the first component of the catalyst as previously described; however, good results were also obtained in which a Lewis base was not employed in the first component of the catalyst, as de-scribed hereinafter.

Example Illustrating Catalyst Without Use of Lewis Base in First Component Example I
Catalyst component 1 consisting of magnesium chloride and titanium tetrachloride was prepared by charging 25 g of magnesium chloride (previously dried 6 hours at 800F (426C) and ball milled 24 hours in a vlbrating mill) and 1.04 g of titanium tetrachloride to a 250 ml spherical stainless steel vessel containing about 400 g of 3/8-inch (0.95 cm) stainless steel balls.
The vessel was placed on a vibrating mill and the mlxture milled for 24 hours at ambient pressure and temperature. The product had a calcul~ted titanium tetrachloride content of 4.0 wt. %, the balance being magnesium chloride.
Suitable amounts of component 1 were used in each of the following runs.
In the following polymerization runs, a dry, air-free, 1 gallon (3.8 liter) stirred, stainless steel reactor was generally charged under a propyl-ene vapor flush with the cocatalyst, catalyst, about 0.9 liter hydrogen (STP) and about 3 liters of liquid propylene. Sufficient liquid propylene was addi-tionally charged so that a liquid full reactor at the reaction temperature of 150F (66C) resulted. More specific details are presented later. Polymeri-zation was allowed to take place for 1 hour at 150F with intermittent addi-tion of propylene as required to maintain a liquid full condition. The reactor and contents were then cooled to about 70F (21C), 10 cc of methanol were added and mixed with the contents after which the mixture was drained into a receiver. The`solid polymer was isolated and dried at ambient conditions.

Calculated productivity is given in te~ms of grams polymer produced per gram titanium per hour and in grams polymer produced per gram catalyst component 1 per hour. The triethylaluminumlethyl anisate (TEA/EA) mole ratio -in each run of this example was 2.85:1.
In a control run, run 1, the reactor, at about 150F, was charged under a gaseous propylene flush with EA, TEA, catalyst component 1, hydrogen and liquid propylene in that order. After the reactor and its contents reached 150F the polymerization run was started. TEA was added as a 14 wt. ~ solu-tion in n-hexane.
In invention run 2, the reactor at about 70F was charged under a gaseous propylene flush with diethylaluminum chloride (DEAC), EA, TEA as a 14 wt. % solution in n-hexane, catalyst component 1, hydrogen and about 3 liters of liquid propylene in that orter. The reactor and its contents were brought to 150F with sufficient propylene atded to obtain liquid-full condi-tions. The polymerization time was 1 hour at 150F with intermittent addition -of propylene as required to maintain a liquid-full condition.
Invention run 3 was a repeat of run 2 using the same charging pro-cedure, etc.
Quantities of reactants, atom ratios of Al/Ti and results obtained are given in the following Table I below.

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o~ o o o ~ ,, 8 ,, _, , ___ 1~ CD CO
~- ~ a) ~ o _I ~1 ~ ~ ~o ~ o ~ ~C , , , o~ ~
l ~1 l O
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o ~o o u~ ~ O E~ O O O
~ o ~o o o o ~, ~, ,,U~ U~
o ~ oo o ,~ o~
,~ zl - ~ ~

1069~09 Inspection of the results reveals that the catalyst of the present invention produces about twice as much:polymer per unit~ti~e as the catalyst system containing no DEAC used in the control run, run 1.

t - 23 -

Claims (42)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR PRIVILEGE
IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A catalyst which forms on mixing:
a first component resulting from the admixture of (1) a halogenated bivalent, trivalent or tetravalent titanium compound, (2) a Lewis base and (3 a compound selected from the group consisting of magnesium and manganese di-halide;
a second component wherein said second component is a compound selected from the group consisting of a trialkylaluminum compound and an organoaluminum compound having two or more aluminum atoms bonded to one another by an oxygen or a nitrogen atom;
a third component wherein said third component is a Lewis base; and a fourth component wherein said fourth component is an organoaluminum monohalide represented by the general formula AlR2X wherein the R groups represent alkyl radicals having from 1 to about 12 carbon atoms, said R groups being the same or different, and X represents a halogen atom, and wherein the molar ratio of said second component to said third component is within the range of from about 1:1.5 to about 6:1.

2. The catalyst of claim 1 wherein titanium tetrahalide and magnesium dihalide are admixed to form said first component:
said second component is a trialkylaluminum compound with alkyl groups having from 1 to about 12 carbon atoms and the alkyl groups are the same or different;
wherein the Lewis bases for said first component and said third com-ponent are selected from the group consisting of amines, amides, ethers, esters, ketones, nitriles and phosphines, and said Lewis bases for the first and third components are the same or different; and said fourth component is selected from the group consisting of organoaluminum monochloride and organoaluminum monobromide.

3. The catalyst of claim 1 wherein titanium tetrachloride and magnesium dichloride are admixed to form said first component;
said second component is a trialkylaluminum compound selected from the group consisting of triethylaluminum, trimethylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri(2-ethylhexyl)aluminum, dimethyl-ethylaluminum, tri-n-amylaluminum, tri-n-dodecylaluminum, and mixtures thereof;
wherein the Lewis base for said first component and said third component is an ester represented by the formula wherein R' represents alkyl groups having from 1 to about 4 carbon atoms and R" represents monovalent radicals selected from the group consisting of -F, -Cl, -Br, -I, -OH, -OR', -OOCR', -SH, -NH2, -NR?, -NHCOR', NO2, -CN, -CHO, -COR', -COOR', -CONH2, CONR?, -SO2R', -CF3, and hydrogen; and said fourth component is an organoaluminum monochloride.

4. The catalyst of claim 3 wherein the Lewis bases are selected from the group consisting of ethyl benzoate, ethyl anisate, ethyl p-dimethylaminobenzoate, ethyl p-fluorobenzoate, ethyl p-cyanobenzoate, methylbenzoate, isopropyl p-diethylaminobenzoate, butyl p-fluorobenzoate, n-propyl-p-cyanobenzoate, ethyl p-trifluoromethylbenzoate, methyl p-hydroxybenzoate, ethyl p-methoxycarbonylbenzoate, methyl p-acetylbenzoate, isopropyl p-formylbenzoate, methyl p-nitrobenzoate, ethyl p-carbamoyl-benzoate, methyl p-mercaptobenzoate and mixtures thereof and the fourth component is diethylaluminum chloride.

5. The catalyst of claim 1 further including a solid organic material which is inert to the catalyst components and which is added to the catalyst as a part of said first component.

6. The catalyst of claim 2 further including a solid organic material selected from the group consisting of low molecular weight and polymeric materials which is inert to the catalyst components and which is added to the catalyst as a part of said first component.

7. The catalyst of claim 3 further including a solid organic mate-rial selected from the group consisting of durene, anthracene, hexachloro-benzene, p-dichlorobenzene, naphthalene, polyvinyltoluene, polycarbonate, polyethylene, polypropylene, polystyrene, polymethylmethacrylate and mixtures thereof.

8. The catalyst of claim 5 wherein said first component results from the admixture of titanium tetra-chloride, magnesium dichloride, ethyl benzoate and durene;
said second component is triethylaluminum;
said third component is ethyl anisate; and said fourth component is diethylaluminum chloride.

9. The catalyst of claim 5 wherein said first component comprises from about 35 to about 65 weight percent magnesium or manganese dihalide, from about 10 to about 60 weight percent solid organic material and from about 5 to about 25 weight percent of the combined titanium compound and Lewis base wherein the molar ratio of the titanium compound to Lewis base ranges from about 0.7:1 to about 1.3:1, the molar ratio of the aluminum compound of the second component to the titanium compound of said first component ranges from about 1:1 to about 150:1; and the molar ratio of the fourth component to the titanium compound of said first component ranges from about 0.5:1 to about 200:1.

10. The catalyst of claim 9 wherein the molar ratio of the second component to the titanium compound of the first component ranges from about 25:1 to afiout 125:1; and the molar ratio of the fourth component to the titanium compound of the first component ranges from about 2:1 to about 150:1.

11. A process comprising:
polymerizing alpha-olefins under polymerization conditions employing a catalyst which forms on mixing:
a first component resulting from the admixture of (a) a halogenated bivalent, trivalent or tetravalent titanium compound, (2) a Lewis base and (3) a compound selected from the group consisting of magnesium and manganese di-halide;
said second component comprises (1) a compound selected from the group consisting of a trialkylaluminum compound and an organoaluminum compound having two or more aluminum atoms bonded to one another by an oxygen or a nitrogen atom and (2) a Lewis base; and said third component comprises organoaluminum monohalide represented by the general formula A1R2X wherein the R groups represent alkyl radicals having from 1 to about 12 carbon atoms, said R groups being the same or different, and X represents a halogen atom, and wherein the molar ratio of said second component to said third component is within the range of from about 1:1.5 to about 6:1.

12. The process of claim 11 wherein said alpha-olefins have from about 2 to about 6 carbon atoms per molecule;
titanium tetrahalide and magnesium dihalide are admixed to form said first component;
said second component of said catalyst is a trialkylaluminum compound with alkyl groups having from 1 to about 12 carbon atoms and the alkyl groups are the same or different;
wherein the Lewis bases for said first component and said third component are selected from the group consisting of amines, amides, ethers, esters, ketones, nitriles and phosphines, and said Lewis bases for the first and third components are the same or different; and said fourth component of said catalyst is selected from the group consisting of organoaluminum monochloride and organoaluminum mono-bromide.

13. The process of claim 11 wherein titanium tetrachloride and magnesium dichloride are admixed to form said first component;
said second component of said catalyst is a trialkylaluminum compound selected from the group consisting of triethylaluminum, trimethyl-aluminum, tri-n-propylaluminum, triisobutylaluminum, tri(2-ethylhexyl)-aluminum, dimethylethylaluminum, tri-n-amylaluminum, tri-n-dodecylaluminum, and mixtures thereof;
wherein the Lewis base for said first component and said third component is an ester represented by the formula wherein R' represents alkyl groups having from 1 to about 4 carbon atoms and R" represents monovalent radicals selected from the group consisting of -F, -Cl, -Br, -I, -OH, -OR', -OOCR', -SH, -NH2, -NR2, -NHCOR', NO2, -CN, -CHO, -COR', -COOR', -CONH2, CONR2', -SO2R', -CF3, and hydrogen; and said fourth component of said catalyst is an organoaluminum mono-chloride.

14. The process of claim 13 wherein the Lewis bases are selected from the group consisting of ethyl benzoate, ethyl anisate, ethyl p-dimethylaminobenzoate, ethyl p-fluorobenzoate, ethyl p-cyano-benzoate, methyl benzoate, isopropyl p-diethylaminobenzoate, butyl p-fluorobenzoate, n-propyl-p-cyanobenzoate, ethyl p-trifluoromethylbenzoate, methyl p-hydroxybenzoate, ethyl p-methoxycarbonylbenzoate, methyl p-acetylbenzoate, isopropyl p-formylbenzoate, methyl p-nitrobenzoate, ethyl p-carbamoylbenzoate, methyl p-mercaptobenzoate and mixtures thereof and the fourth component is diethylaluminum chloride.

15. The process of claim 11 wherein said catalyst further includes a solid organic material which is inert to the catalyst compo-nents and which is added to the catalyst as a part of said first component.

16. The process of claim 12 wherein the catalyst further includes a solid organic material selected from the group consisting of low molecular weight and polymeric materials which is inert to the catalyst components and which is added to the catalyst as a part of said first component.

17. The process of claim 13 wherein the catalyst further includes a solid organic material selected from the group consisting of durene, anthracene, hexachlorobenzene, p-dichlorobenzene, naphthalene, polyvinyltoluene, polycarbonate, polyethylene, polypropylene, polystyrene, polymethylmethacrylate and mixtures thereof.

18. The process of claim 15 wherein said first component of said catalyst results from the admixture of titanium tetrachloride, magnesium dichloride, ethyl benzoate and durene;
said second component of said catalyst is triethylaluminum;
said third component is ethyl anisate; and said fourth component is diethylaluminum chloride.

19. The process of claim 15 wherein said first component of said catalyst comprises from about 35 to about 65 weight percent magnesium or manganese dihalide, from about 10 to about 60 weight percent solid organic material and from about 5 to about 25 weight percent of the combined titanium compound and Lewis base wherein the molar ratio of the titanium compound and Lewis base ranges from about 0.7:1 to about 1.3:1;
the molar ratio of the aluminum compound of the second component to the titanium compound of said first component ranges from about 1:1 to about 150:1; and the molar ratio of the fourth component to the titanium compound of said first component ranges from about 0.5:1 to about 200:1.

20. The process of claim 19 wherein the molar ratio of the second component of said catalyst to the titanium compound of the first component of said catalyst ranges from about 25:1 to about 125:1; and the molar ratio of the fourth component to the titanium compound of the first component ranges from about 2:1 to about 150:1.

21. The process of claim 11 wherein the alpha-olefins are selected from the group consisting of ethylene and propylene.

22. The process of claim 11 wherein the polymerization temperature ranges from about 60 to about 212° F (15.5 to 100°C), the polymerization pres-sure is one which maintains the alpha-olefins in the liquid phase, and the components of the catalyst are mixed together at a temperature in the range of from about -120°F to about 80°F (-84°C to 27°C).

23. The process of claim 15 wherein the alpha-olefin is propylene, the polymerization temperature ranges from about 75 to about 175°F (24° to 80°C), and the polymerization pressure is one which maintains the propylene in the liquid phase.

24. The process of claim 23 wherein the polymerization tempera-ture ranges from about 120 to about 160°F (49° to 71°C).

CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE:

25. A catalyst which forms on mixing:
a first component resulting from the admixture of a halogenated bivalent, trivalent or tetravalent titanium compound, and a compound selected from the group consisting of magnesium and manganese dihalide;
a second component wherein said second component is a compound selected from the group consisting of a trialkylaluminum compound and an organoaluminum compound having two or more aluminum atoms bonded to one another by an oxygen or a nitrogen atom;
a third component wherein said third component is a Lewis base; and a fourth component wherein said fourth component is an organoaluminum monohalide represented by the general formula A1R2X wherein the R groups represent alkyl radicals having from 1 to about 12 carbon atoms, said R groups being the same or different, and X represents a halogen atom, and wherein the molar ratio of said second component to said third component is within the range of from about 1:1.5 to about 6:1.

26. The catalyst of claim 25 wherein titanium tetrahalide and magnesium dihalide are admixed to form said first component;
said second component is a trialkylaluminum compound with alkyl groups having from 1 to about 12 carbon atoms and the alkyl groups are the same or different;
wherein the Lewis base for said third component is selected from the group consisting of amines, amides, ethers, esters, ketones, nitriles and phosphines; and said fourth component is selected from the group consisting of organoaluminum monochloride and organoaluminum monobromide.

27. The catalyst of claim 25 wherein titanium tetrachloride and magnesium dichloride are admixed to form said first component;
said second component is a trialkylaluminum compound selected from the group consisting of triethylaluminum, trimethylaluminum, tri-n-propyl-aluminum, triisobutylaluminum, tri(2-ethylhexyl)aluminum, dimethylethylaluminum,tri-n-amylaluminum, tri-n-dodecylaluminum, and mixtures thereof;

wherein the Lewis base for said third component is an ester repre-sented by the formula wherein R' represents alkyl groups having from 1 to about 4 carbon atoms and R" represents monovalent radicals selected from the group consiting of -F, -Cl, -Br, -I, -OH, -OR', -OOCR', -SH, -NH2, -NR'2, -NHCOR', NO2, -CN, -CHO, -COR', -COOR', -CONH2, CONR'2, -SO2R', -CF3, and hydrogen; and said fourth component is an organoaluminum monochloride.

28. The catalyst of claim 27 wherein the Lewis base is selected from the group consisting of ethyl benzoate, ethyl anisate, ethyl p-dimethyl-aminobenzoate, ethyl p-fluorobenzoate, ethyl p-cyanobenzoate, methylbenzoate, isopropyl p-diethylaminobenzoate, butyl p-fluorobenzoate, n-propyl-p-cyano-benzoate, ethyl p-trifluoromethylbenzoate, methyl p-hydroxybenzoate, ethyl p-methoxycarbonylbenzoate, methyl p-acetylbenzoate, isopropyl p-formylbenzo-ate, methyl p-nitrobenzoate, ethyl p-carbamoylbenzoate, methyl p-mercapto-benzoate and mixtures thereof and the fourth component is diethylaluminum chloride.

29. The catalyst of claim 25 further including a solid organic material which is inert to the catalyst components and which is added to the catalyst as a part of said first component.

30. The catalyst of claim 29 wherein the solid organic material is selected from the group consisting of low molecular weight and polymeric materials.

31. The catalyst of claim 29 wherein the solid organic material is selected from the group consisting of durene, anthracene, hexachlorobenzene, p-dichlorobenzene, naphthalene, polyvinyltoluene, polycarbonate, polyethylene, polypropylene, polystyrene, polymethylmethacrylate and mixtures thereof.

32. The catalyst of claim 25 wherein said first component results from the admixture of titanium tetra-chloride and magnesium dichloride;
said second component is triethylaluminum;
said third component is ethyl anisate; and said fourth component is diethylaluminum chloride.

33. The catalyst of claim 25 wherein said first component results from the admixture of titanium tetra-chloride, magnesium dichloride and durene;
said second component is triethylaluminum;
said third component is ethyl anisate; and said fourth component is diethylaluminum chloride.

34. A process comprising:
polymerizing alpha-olefins under polymerization conditions employing a catalyst which forms on mixing:
a first component resulting from the admixture of a halogenated bivalent, trivalent or tetravalent titanium compound, and a compound selected from the group consisting of magnesium and manganese dihalide;
a second component wherein said second component is a compound selected from the group consisting of a trialkylaluminum compound and an organoaluminum compound having two or more aluminum atoms bonded to one another by an oxygen or a nitrogen atom;
a third component wherein said third component is a Lewis base; and a fourth component wherein said fourth component is an organoaluminum monohalide represented by the general formula A1R2X wherein the R groups represent alkyl radicals having from 1 to about 12 carbon atoms, said R groups being the same or different, and X represents a halogen atom, and wherein the molar ratio of said second component to said third component is within the range of from about 1:1.5 to about 6:1.

35. The process of claim 34 wherein said alpha-olefins have from about 2 to about 6 carbon atoms per molecule;
titanium tetrahalide and magnesium dihalide are admixed to form said first component;
said second component of said catalyst is a trialkylaluminum compound with alkyl groups having from 1 to about 12 carbon atoms and the alkyl groups are the same or different;
wherein the Lewis base for said third component is selected from the group consisting of amines, amides, ethers, esters, ketones, nitriles and phosphines; and said fourth component of said catalyst is selected from the group consisting of organoaluminum monochloride and organoaluminum monobromide.

36. The process of claim 34 wherein titanium tetrachloride and magnesium dichloride are admixed to form said first component;
said second component of said catalyst is a trialkylaluminum compound selected from the group consisting of triethylaluminum, trimethylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri(2-ethylhexyl)aluminum, dimethyl-ethylaluminum, tri-n-amylaluminum, tri-n-dodecylaluminum, and mixtures thereof;
wherein the Lewis base for said third component is an ester repre-sented by the formula wherein R' represents alkyl groups having from 1 to about 4 carbon atoms and R" represents monovalent radicals selected from the group consisting of -F, -Cl, -Br, -I, -OH, -OR', -OOCR', -SH, -NH2, -NR'2, -NHCOR', NO2, -CN, -CHO, -COR', -COOR', -CONH2, CONR'2, -SO2R', -CF3, and hydrogen; and said fourth component of said catalyst is an organoaluminum mono-chloride.

37. The process of claim 36 wherein the Lewis base is selected from the group consisting of ethyl benzoate, ethyl anisate, ethyl p-dimethyl-aminobenzoate, ethyl p-fluorobenzoate, ethyl p-cyanobenzoate, methylbenzoate, isopropyl p-diethylaminobenzoate, butyl p-fluorobenzoate, n-propyl-p-cyano-benzoate, ethyl p-trifluoromethylbenzoate, methyl p-hydroxybenzoate, ethyl p-methoxycarbonylbenzoate, methyl p-acetylbenzoate, isopropyl p-formylbenzoate, methyl p-nitrobenzoate, ethyl p-carbamoylbenzoate, methyl p-mercaptobenzoate and mixtures thereof and the fourth component is diethylaluminum chloride.

38. The process of claim 34 wherein said catalyst further includes a solid organic material which is inert to the catalyst components and which is added to the catalyst as a part of said first component.

39. The process of claim 38 wherein the solid organic material is selected from the group consisting of low molecular weight and polymeric materials.

40. The process of claim 38 wherein the solid organic material is selected from the group consisting of durene, anthracene, hexachlorobenzene, p-dichlorobenzene, naphthalene, polyvinyltoluene, polycarbonate, polyethylene, polypropylene, polystyrene, polymethylmethacrylate and mixtures thereof.

41. The process of claim 34 wherein said alpha-olefin is propylene;
said first component of said catalyst results from the admixture of titanium tetrachloride and magnesium dichloride;
said second component of said catalyst is triethylaluminum;
said third component is ethyl anisate; and said fourth component is diethylaluminum chloride.

42. The process of claim 34 wherein said alpha-olefin is propylene;
said first component of said catalyst results from the admixture of titanium tetrachloride, magnesium dichloride and durene;
said second component of said catalyst is triethylaluminum;
said third component is ethyl anisate; and said fourth component is diethylaluminum chloride.