US 4,707,530 AGrant
Polymerization Catalyst
Issue Date:1987-11-17
•14 Claims
Abstract
Ethylene is homopolymerized or copolymerized with another olefin monomer in the presence of a catalyst system comprising organo metal cocatalyst and a titanium-containing catalyst component, said titanium-containing catalyst component being obtained by reacting together a porous particulate material, an organic magnesium compound, a halogen or interhalogen compound and titanium tetrachloride.
Metadata
Assignee
- Exxon Research & Engineering Co.
Inventor
- Burnett H. Johnson
Application Information
Application Number:US 5916348
Filing Date:1984-04-26
Priority Date:1981-09-30
Art Unit:155
Classifications
IPC:
C08F 402C08F 1002
Field of Search:
52697;121;124;129;137
Patent Drawings
This patent does not have any drawings.
Description
EXAMPLE 1
Catalyst Preparation
A 3 g portion of the dried dehydrated silica gel was weighed under ultra anhydrous conditions in a dry glass vessel equipped with a stirrer and 75 ml of a purified mineral oil was added and stirred to mix well. 6.5 ml of a solution of butylethylmagnesium (BEM) comprising 0.69 mmol BEM and 0.01 mmol triethylaluminum (TEAL) in n-heptane was added dropwise at ambient temperature to the silica slurry while stirring vigorously. After stirring for 10 minutes, the slurry was allowed to stand for 20 minutes.
A 2 ml portion of a solution of TiCl.sub.4 in n-hexane containing 1.5 mmol TiCl.sub.4 per ml of solution was slowly added to the slurry of silica supported BEM at ambient temperature while stirring vigorously. The particles of silica gel turned dark brown and no color was detected in the supernatant mineral oil. Titanium constituted 3.7% by weight of the total solids reaction product.
One-half of the reaction product slurry was transferred to a pressure tight glass vessel, equipped with a stirrer, which was connected to a source of dry chlorine gas. The vessel was purged with the Cl.sub.2 gas to remove the N.sub.2 blanket over the slurry and thereafter the vessel was pressured to 7.5 psig with Cl.sub.2. The slurry was stirred vigously for 3 hours after which the unreacted Cl.sub.2 was removed by connecting the vessel to a vacuum source. The vessel was then pressured up with dry N.sub.2.
Polymerization
Polymerizations using the reaction product and the halogenated reaction product were performed in a 1.5 liter stainless steel stirred reactor. 875 ml of hexane was added to the reactor and the reactor was thereafter heated to 85.degree. C. 2.3 mmol of triisobutylaluminum (TIBAL) cocatalyst was added as a solution in n-heptane to the reactor. A weighed portion of catalyst was then added to the reactor. 45 psig of H.sub.2 pressure was introduced to the reactor. Polymerization was initiated by introduction of ethylene at a pressure of 75 psi and constant total pressure was maintained by flow of ethylene into the reactor on demand. The polymerizations were terminated after one hour. The results of the polymerization are summarized in Table 1.
The results demonstrate that the catalyst of this invention has about five times the activity, a significantly improved response to H.sub.2 for melt index control and produces a resin having a higher bulk density as compared with the results of the non-halogenated reaction product catalyst.
EXAMPLES 2 A, B AND C AND COMPARATIVE EXAMPLES 2A, B AND C
The objective of these examples is to show that various alkyl magnesium/aluminum complexes are highly effective for the preparation of catalyst in accordance with the invention.
The solids reaction product A, B and C were prepared in the manner as described in Example 1 except the alkyl metal components were reacted with the silica gel support for one hour before adding TiCl.sub.4. Solids A comprised BEM(TEAL) in a ratio of 1:0.014, solids B comprised di-n-butylmagnesium (DNBM)/TEAL in a ratio of 1:0.13 and solids C comprised DNBM/TEAL in a ratio of 1:1.75. The chlorinated catalyst A, B and C were prepared by treatment of the solids with Cl.sub.2 gas in the manner as described in Example 1. Employing the amount of catalyst as summarized in Table II, polymerizations were conducted under the conditions as described in Example 1. The results are summarized in Table II. The results demonstrate that the three catalysts were substantially improved by chlorinating with Cl.sub.2 gas with the lower aluminum content catalysts being the preferred compositions.
EXAMPLES 3A, B AND C AND COMPARATIVE EXAMPLES 3A, B AND C
These Examples demonstrate that various transition metal compounds can be usefully employed for the preparation of catalysts of this invention.
Three different transition metal compounds, listed in Table III were used to prepare the catalysts. Employing (BEM)(TEAL).sub.0.014 the solids reaction product were prepared as in Example 1. The mole ratio of BEM to transition metal component was 1.5 in each case. Portions of the supported catalyst were treated with chlorine gas for 1 hour at 7.5 psig to produce catalyst coponents in accordance with the invention. The solids A, B and C and the catalysts A, B and C prepared in accordance with the invention were evaluated by polymerization of ethylene. Employing the amount of catalyst as listed in Table III ethylene polymerizations were carried out under the conditions as in Example 1. The results of the polymerizations are summarized in Table III. Productivities were greatly increased in each case where the chlorine treatment was employed.
EXAMPLE 4
This example demonstrates the superiority of halogens over hydrogen halides for preparing the catalysts of this invention.
One portion of the solids reaction products prepared as in Example 1 was treated with HCl gas for 18 hours at 7.5 psig. Another portion of the solids reaction product was treated with Cl.sub.2 gas for 1 hour at 7.5 psig to produce a catalyst component in accordance with the invention.
The solids reaction product, the HCl treated reaction product and the catalyst prepared in accordance with the invention were compared by polymerizing ethylene as described in Example 1. The results of the polymerizations are summarized in Table IV. Treatment with Cl.sub.2 gas increased productivity, H.sub.2 response as indicated by melt index and improved bulk density to a much greater extent than does treatment of the solids reaction product with HCl.
EXAMPLE 5
The objective of this example is to show that even after treating exhaustively a solids reaction product as prepared in Example 1 with HCl, a very large improvement in catalyst performance can be achieved by subsequent treatment with Cl.sub.2 gas.
A portion of the solids reaction product prepared as in Example 1, was treated with HCl gas for 24 hours at 7.5 psig HCl to produce a HCl treated solids reaction product. This catalyst was used to polymerize ethylene under conditions as in Example 1 with the results shown in Table V as Comparative 5.
The remaining HCl treated solids reaction product was treated with Cl.sub.2 gas for 3 hours at 7.5 psig Cl.sub.2 to produce a catalyst in accordance with the invention. Ethylene was polymerized under conditions as in Example 1. The results are summarized in Table V as invention Example 5.
EXAMPLE 6
The purpose of this example is to show that different orders of addition of alkylmagnesium compound and transition metal compound to the silica gel support can be employed in preparing the catalysts of this invention.
A solids reaction product was prepared using the procedure of Example 1 by treating a 3.0 g portion of silica gel with 4.5 mmol of BEM and allowing the material to react for 30 minutes at ambient temperature. 1.5 mmol of TiCl.sub.4 was then added and stirring was continued for 5 minutes. This catalyst is labeled Solids A.
A second solids catalyst was prepared except 1.5 mmol of TiCl.sub.4 was initially added to 3.0 gms of silica support and reacted for 30 minutes after which 4.5 mmol of BEM were added and stirred for 5 minutes. This catalyst is labeled Solids B.
Portions of Solids A and B were subsequently chlorinated using Cl.sub.2 at 7.5 psig for 3 hours at ambient temperature and labeled Catalyst A and B respectively.
Ethylene was polymerized in the manner and under conditions as described in Example 1 using solids A and B and Inventio Catalysts A and B. The polymerization results are summarized in Table VI.
EXAMPLE 7
The objective is to show that unsupported catalysts are greatly improved by the halogen treatment in accordance with this invention.
A stirred glass vessel containing 90 ml of hexane was cooled to -5.degree. C. under a blanket of dry N.sub.2. Dilute solutions containing 3 mmols of TiCl.sub.4 in hexane and 3 mmols of (BEM)(TEAL).sub.0.17 complex were added dropwise and simultaneously to the cold hexane over a time period of 80 minutes. A dark brown catalyst precipitated as the addition proceeded. The resulting catalyst slurry was allowed to warm to room temperature and then to age for 24 hours at ambient temperature under a blanket of dry N.sub.2. This unsupported comparative catalyst is identified as Solids A.
A portion of Solids A was subsequently treated with Cl.sub.2 treated ctalyst of this invention were employed to polymerize ethylene in the manner of Example 1. The results of polymerization are summaried in Table VII.
Each catalyst contained approximately 18% by weight of titanium.
EXAMPLE 8
The objective of this example is to demonstrate that the halogenated catalysts of this invention are well suited for the preparation of low density polyethylene copolymers.
A reaction product was prepared exactly as in Example 1 and was treated with Cl.sub.2 gas for 1 hour at atmospheric pressure. The resulting catalyst was used to copolymerize ethylene and butene-1.
The polymerization was conducted as in Example 1 except that, after addition of the triisobutylaluminum cocatalyst, 50 g of butene-1 were added to the reactor. The reactor was pressured with 45 psi H.sub.2 after which 45 psi of ethylene pressure was introduced, a constant total pressure was maintained for 60 minutes and the temperature controlled to 85.degree. C. The results are presented in Table VIII.
The following example and comparative example demonstrate that Cl.sub.2 can be added to the reaction vessel prior to other reactive ingredients so long as chlorine is available during the last step of catalyst preparation.
EXAMPLE 9
Catalyst Preparation
A 3.5 gram portion of dehydrated silica gel was weighed under anhydrous conditions into a 125 cc. septum vial equipped with a stirring bar. 75 ml of dried degassed hexane was added via a syringe and the suspension stirred well.
The vessel was connected to a source of dry Cl.sub.2 gas and purged to remove residual nitrogen. Chlorination was continued for 1 hour under a Cl.sub.2 pressure of 7.5 psig. The chlorine atmosphere was then replaced by purging the vial with nitrogen for 0.5 hour. 9.2 ml of a solution of BEM comprising 0.69 mmol BEM was added dropwise at ambient temperature to the slurry while stirring vigorously. Stirring was continued for 1 hour.
A 2.1 ml portion of a solution of TiCl.sub.4 in hexane containing 1.0 mmol TiCl.sub.4 per ml of solution was slowly added to the slurry of silica supported BEM at ambient temperature while stirring vigorously. Stirring was continued for 1 hour. The catalyst was then filtered, washed with hexane and dried in vacuo.
Polymerization
Employing the amounts of catalyst as summarized in Table IX, polymerizations were conducted under conditions as in Example 1. The results as summarized in Table IX demonstrate that the addition of chlorine into the catalyst preparation vessel prior to the addition of BEM and TiCl.sub.4 results in the production of an highly active polymerization catalyst.
EXAMPLE 9
Comparative
Catalyst Preparation
A 3.5 gram portion of dehydrated silica gel was weighed under anhydrous conditions into a 125 cc. septum vial equipped with a stirring bar. 75 ml of dried degassed hexane was added via a syringe and the suspensions stirred well. The vessel was connected to a source of dry Cl.sub.2 gas and purged to remove residual nitrogen. Chlorination was continued for 1 hour under a Cl.sub.2 pressure of 7.5 psig. The chlorine atmosphere was then replaced by purging the vial with nitrogen for 0.5 hour. The chlorine treated silica was filtered, washed with hexane and dried in vacuo. 3.2 grams of the treated silica was recovered.
To the treated silica [above] was added 75 cc of dried degassed hexane and the resulting slurry stirred vigorously. 8.3 ml of a solution of BEM comprising 0.69 mmol BEM was added dropwise at ambient temperature to the slurry while stirring vigorously. Stirring was continued for 1 hour.
A 1.9 ml portion of a solution of TiCl.sub.4 in hexane containing 1.0 mmol TiCl.sub.4 per ml of solution was slowly added to the slurry of silica supported BEM at ambient temperature while stirring vigorously. Stirring was continued for 1 hour. The catalyst was then filtered, washed with hexane and dried in vacuo.
Polymerization
Ethylene was polymerized under identical condition as in Example 9. The results as summarized in Table IX show that by washing the chlorinated silica (thereby removing available chlorine) prior to the addition of BEM and TiCl.sub.4 poor results are obtained.
EXAMPLE 10
Catalyst Preparation
A 3.5 gram portion of dehydrated silica gel was weighed under anhydrous conditions into a 125 cc septum vial equipped with a stirring bar. 75 ml of dried degassed hexane was added via a syringe and the suspension stirred well. 9.2 ml of a solution of BEM comprising 0.69 mmol BEM was added dropwise at ambient temperature to the slurry while stirring vigorously. Stirring was continued for 1 hour.
The vessel was connected to a source of dry Cl.sub.2 gas and purged to remove residual nitrogen. Chlorination was continued for 1 hour under a Cl.sub.2 pressure of 7.5 psig. The chlorine atmosphere was then replaced by purging the vial with nitrogen for 0.5 hour.
A 2.1 ml portion of a solution of TiCl.sub.4 in hexane containing 1.0 mmol TiCl.sub.4 per ml of solution was slowly added to the slurry of silica supported BEM at ambient temperature while stirring vigorously. Stirring was continued for 1 hour. The catalyst was then filtered, washed with hexane and dried in vacuo.
Polymerization
Ethylene was polymerized under identical conditions as in Example 9. The conditions and results are summarized in Table IX.
EXAMPLE 11
The following examples demonstrate that halogens are unexpectedly superior to halide containing compound with respect to improving the activity and productivity of ethylene polymerization catalyst.
EXAMPLE 11
Comparative
Catalyst Preparation
A 3.5 gram portion of dehydrated silica gel was weighed under anhydrous conditions into a 125 cc septum vial equipped with a stirring bar. 75 ml of dried degassed heane was added via a syringe and the suspension stirred well.
9.2 ml of a solution of BEM comprising 0.69 mmol BEM was added dropwise at ambient temperature to the slurry while stirring vigorously. Stirring was continued for 1 hour.
A 2.1 ml portion of a solution of TiCl.sub.4 in hexane containing 1.0 mmol TiCl.sub.4 per ml of solution was slowly added to the slurry of silica supported BEM at ambient temperature while stirring vigorously. Stirring was continued for 1 hour.
A 10 ml portion of neat SiCl.sub.4 containing 0.87 mmol SiCl.sub.4 per ml was added to the sitring catalyst slurry. This slurry was stirred for an additional hour at ambient temperature. The final catalyst was then filtered, washed with hexane and dried in vacuo
Polymerization
Ethylene was polymerized under identical conditions as Example 9. The conditions and results are summerized in Table IX.
EXAMPLE 12
Catalyst Preparation
A 3.5 gram portion of dehydrated silica gel was weighed under anhydrous conditions into a 125 cc septum vial equipped with a stirring bar. 75 ml of dried degassed hexane was added via a syringe and the suspension stirred well.
9.2 ml of a solution of BEM comprising 0.69 mmol BEM was added dropwise at ambient temperature to the slurry while stirring vigorously. Stirring was continued for 1 hour.
A 2.1 ml portion of a solution of TiCl.sub.4 in hexane containing 1.0 mmol TiCl.sub.4 per ml of solution was slowly added to the slurry of silica supported BEM at ambient temperature while stirring vigorously. Stirring was continued for 1 hour.
A 10 ml portion of neat SiCl.sub.4 containing 0.87 mmol SiCl.sub.4 per ml was added to the stirring catalyst slurry. This slurry was stirred for an additional hour at ambient temperature.
The vessel was connected to a source of dry Cl.sub.2 gas and purged to remove residual nitrogen. Chlorination was continued for 1 hour under a Cl.sub.2 pressure of 7.5 psig. The chlorine atmosphere was then replaced by purging the vial with nitrogen for 0.5 hour. The final catalyst was then filtered, washed with hexane and dried in vacuo.
Polymerization
Ethylene was polymerized under identical conditions as Example 11. The conditions and results are summarized in Table 1X. The results demonstratively show that the activity and productivity of a SiCl.sub.4 treated catalyst is unexpectedly improved by further treatment with a halogen.
EXAMPLE 13
Comparative
Catalyst Preparation
A 3.5 gram portion of dehydrated silica gel was weighed under anhydrous conditions into a 125 cc septum vial equipped with a stirring bar. 75 ml of dried degassed hexane was added via a syringe and the suspension stirred well.
9.2 ml of a solution of BEM comprising 0.69 mmol BEM was added dropwise at ambient temperature to the slurry while stirring vigorously. Stirring was continued for 1 hour.
A solution containing a one to one molar ratio of TiCl.sub.4 and CCl.sub.4 was prepared and stirred for 0.5 hour at ambient temperature. A 2.1 ml portion of this solution containing 1.0 mmol TiCl.sub.4 per ml of solution was slowly added to the slurry of silica supported BEM at ambient temperature while stirring vigorously. Stirring was continued for 1 hour. The catalyst was filtered, washed with hexane and dried in vacuo.
Polymerization
Ethylene was polymerized under identical conditions as Example 11. The conditions and results are sumamrized in Table IX.
EXAMPLE 14
A 3.5 gram portion of dehydrated silica gel dried at 600.degree. C under N.sub.2 was weighed under anhydrous conditions into a 125 cc. septum vial equipped with a stirring bar. 75 ml of dried degassed hexane was added via a syringe and the suspension stirred well.
9.2 ml of a solution of BEM comprising 0.69 mmol BEM was added dropwise at ambient temperature to the slurry while stirring vigorously. Stirring was continued for 1 hour.
A 2.1 ml portion of a solution of TiCl.sub.4 in hexane containing 1.0 mmol TiCl.sub.4 per ml of solution was slowly added to the slurry of silica supported BEM at ambient temperature while stirring vigorously. Stirring was continued for 1 hour.
The vessel was connected to a source of dry Cl.sub.2 gas and purged to remove residual nitrogen. Chlorination was continued for 1 hour under a Cl.sub.2 pressure of 7.5 psig. The chlorine atmosphere was then replaced by purging the vial with nitrogen for 0.5 hour. The final catalyst was filtered, washed with hexane and dried in vacuo. The final catalyst contained 2.2% titanium.
Polymerization
Ethylene was polymerized under identical conditions as in Example 9. The conditions and results are summarized in Table IX.
EXAMPLE 15
Catalyst Preparation
A 3.5 gram portion of silica gel dried at 600.degree. C. under N.sub.2 was weighed under anhydrous conditions into a 125 cc. septum vial equipped with a stirring bar. 75 ml of dried degassed hexane was added via a syringe and the suspension stirred well.
The vessel was connected to a source of dry Cl.sub.2 gas and purged to remove residual nitrogen. Chlorination was continued for 1 hour under a Cl.sub.2 pressure of 7.5 psig. The chlorine atmosphere was then replaced by purging the vial with nitrogen for 0.5 hour. 9.2 ml of a solution of butylethylmagnesium (BEM) comprising 0.69 mmol BEM was added dropwise at ambient temperature to the slurry while stirring vigorously. After stirring for 1 hour, the catalyst was filtered, washed with hexane and dried in vacuo.
Approximately half of the above dry solid (1.85 grams) was reslurried in 35 cc of hexane. The remaining solid was used in the example below. The stirred slurry was then treated with 1.0 cc of a 1 mmole TiCl.sub.4 /cc of hexane solution. Stirring was continued for 1 hour. The catalyst was then filtered, washed with hexane and dried in vacuo.
Polymerization
Ethlene was polymerized under identical conditions as in Example 9. The condition and results are summarized in Table IX.
EXAMPLE 16
Catalyst Preparation
The remaining portion of the dry solid obtained in the preparation for Example 15 above was reslurried in 35 cc of hexane in a 125 cc vial. The vessel was connected to a source of dry Cl.sub.2 gas and purged to remove residual nitrogen. Chlorination was continued for 1 hour under a Cl.sub.2 pressure of 7.5 psig. The chlorine atmosphere was then replaced by purging the vial with nitrogen for 0.5 hour.
A 1.0 ml portion of a solution of TiCl.sub.4 in hexane containing 1.0 mmol TiCl.sub.4 per ml of solution was slowly added to the slurry at ambient temperature while stirring vigorously. Stirring was continued for 1 hour after which time the catalyst was filtered, washed with hexane and dried in vacuo.
Polymerization
Ethylene was polymerized under identical conditions as in Example 9. The conditions and results are summarized in Table IX.
EXAMPLE 17
A 1000 gram portion of Davison 952 silica was dehydrated at 600.degree. C. This silica was added to a 10-liter catalyst preparation vessel equipped with a mechnical agitator. 2000 cc of isopentane was then added and the agitation started. 2817 cc of a solution of 10% (wt) BEM in heptane was then added while maintaining the mixture at 45.degree. C. After the addition was complete an additional 1000 cc of isopentane was added and the mixture agitated for 4 hours. At this point, 37.9 gms of TiCl.sub.4 was added and the mixture reacted for one hour at 45.degree. C. Following this period, the nitrogen atmosphere in the vessel was replaced by Cl.sub.2 gas. The Cl.sub.2 pressure was maintained at 7.5 psig for 1.5 hours at 45.degree. C. after which the Cl.sub.2 was displaced by N.sub.2. The final catalyst was recovered by heating the vessel to a jacket temperature of 75.degree. C. while decreasing the N.sub.2 pressure to 2 psig and venting the volatilized isopentane solvent. The dry catalyst was recovered under an N.sub.2 atmosphere.
A 36 inch internal diameter fluidized bed reactor vessel, operated in a continuous manner, was used to produce an ethylene, butene-1 copolymer. A reaction mixture comprising ethylene, butene-1 and hydrogen was circulated continuously through the bed at a superficial velocity estimated to be about three to four times the minimum necessary for fluidization. In the fluidized bed, the reaction temperature was controlled at 75.degree. C. by adjusting the temperature of the gas fed to the fluidized bed reactor vessel using a heat exchanger in the circulating gas loop. Aluminum triethyl was pumped continuously into the reactor as a 11% (wt) solution in isopentane. The solid catalyst described above was blown into the reactor as a dry powder in a stream of nitrogen so as to maintain a rate of polymer production of about 150 lb/hr, which corresponds to a mean residence time of four hours. The reaction pressure was maintained automatically by admitting an ethylene/hydrogen mixture through a control valve. Liquid butene-1 was pumped into the circulating gas stream so as to maintain a constant composition as determined by Gas-Liquid Chromotography. The polymer formed was removed periodically so as to maintain an essentially constant level in the reactor vessel. The polymer collected was degassed in a stream of nitrogen. Polymer was produced at the rate of 150 lbs/hr. The polymer had a melt index of 1.49 dg/min.
Claims
What is claimed is:
1. A process for polymerizing ethylene which comprises polymerizing ethylene, a mixture of ethylene and other alpha-olefins, or a mixture of ethylene, other alpha-olefins and/or diolefins in the presence of a catalyst system comprising a catalyst component (I) obtained by contacting silica in an inert solvent, (A) at least one organomagnesium compound, (B) at least one titanium compound represented by the formula TiX'.sub.4-q (OR').sub.q wherein X' is halogen, R' is a hydrocarbyl or substituted hydrocarbyl group having from 1-20 carbon atoms, and q is 0 or a number equal to or less than 4 wherein the titanium content is in the range of about 0.02 to about 3 mmols per gram of said silica, and at any state of the contacting, (C) a sufficient amount of chlorine such that after said silica is contacted with said organomagnesium compound and the titanium compound, chlorine is available so that the activity of the catalyst is increased, and (II) an organoaluminum compound of the formula AlR".sub.n X".sub.3-n wherein R" is hydrogen, hydrocarbyl or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen and n is a number from 1 to 3; and recovering ethylene polymer of higher bulk density than when chlorine is not available.
2. The process in accordance with claim 1 wherein the silica is contacted in separate stages with (A) the organomagnesium compound represented by the formula: wherein R is a hydrocarbyl group having from 1 to 20 carbon atoms, X is a halogen or alkoxide or mixtures thereof, x is greater than 0 and the ratio of y/x+y is from 0 to 1.
3. The process in accordance with claim 2 wherein the titanium compound is TiCl.sub.4.
4. The process in accordance with claim 1 wherein the contacting with the silica is in the sequential order of, (1) organomagnesium compound, (2) titanium containing compound and (3) chlorine.
5. The process in accordance with claim 1 wherein the contacting with the silica is in the sequential order of (1) chlorine, (2) organomagnesium compound and (3) titanium compound.
6. The process in accordance with claim 1 wherein the halogen compound is contacted continuously.
7. The process in accordance with claim 2 wherein chlorine is contacted with a product recovered from the contacting of the organomagnesium compound and titanium compound with the silica.
8. The process of claim 2 wherein y/x+y is from 0 to about 0.7.
9. The process of claim 8 wherein y/x+y is from 0 to about 0.1.
10. A continuous catalytic process for producing ethylene polymers selected from the group consisting of ethylene homopolymers and ethylene copolymers with at least one C.sub.3 to C.sub.8 alpha-olefin in the presence of a titanium containing catalyst in a fluid bed reactor under a pressure of less than 1,000 psi in the gas phase which comprises polymerizing ethylene along or with at least one C.sub.3 to C.sub.8 alpha-olefin at a temperature in the range of about 30.degree. to about 105.degree. C. by contacting the monomer charge with, and in the presence of about 0 to about 2.0 moles of hydrogen per mole of ethylene in the gas phase reaction zone, the catalyst comprising (A) and alkyl aluminum co-catalyst and (B) a titanium containing catalyst obtained by contacting silica in an inert solvent in separate stages with (a) at least one organomagnesium compound, (b) at least one titanium compound represented by the formula TiX'.sub.4-q (OR').sub.q wherein X' is halogen, R' is a hydrocarbyl or substituted hydrocarbyl group having from 1-20 carbon atoms, and q is 0 or a number equal to or less than 4, and at any stage of the contacting, (c) a sufficient amount of chlorine such that after said silica is contacted with said organomagnesium compound and said titanum compound, chlorine is available so that the activity of the catalyst is increased, and wherein the titanium content is in the range of about 0.02 to about 3 mmols per gram of silica; and recovering ethylene polymer of higher bulk density than when chlorine is not available.
11. The continuous catalytic process of claim 10 wherein the organomagnesium compound is represented by the formula: wherein R is a hydrocarbyl or substituted hydrocarbyl group having from 1 to about 20 carbon atoms, X is a halogen or alkoxide or mixtures thereof, n is 1 to 3, x is greater than 0 and the ratio of y/x+y is from 0 to 1.
12. A process for the homopolymerization or copolymerization of ethylene comprising homopolymerizing ethylene or copolymerizing ethylene with one or more alpha-olefins and/or diolefins in the presence of a catalyst system comprising (I) the solid reaction product obtained by contacting in an inert solvent (a) silica, (b) ((n--C.sub.4 H.sub.9)(C.sub.2 H.sub.5)Mg)((C.sub.2 H.sub.5).sub.3 Al).sub.y wherein y is zero to about 2, (c) TiCl.sub.4, and (d) a sufficient amount of Cl.sub.2 such that after said silica is contacted with said components (b) and (c), chlorine is available so that the activity of the catalyst is increased; and (II) an organoaluminum compound of the formula AlR".sub.n X".sub.3-n wherein R" is hydrogen, hydrocarbyl, or substituted hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen, and n is 1 to 3; and recovering polymer of higher bulk density than when chlorine is not available.
13. The process of claim 12 wherein the reactants are contacted in the sequential order of (a), (b), (c) and (d).
14. A process for the polymerization of ethylene which comprises polymerizing ethylene, a mixture of ethylene and other alpha-olefins, or a mixture of ethylene, other alpha-olefins and/or diolefins in the presence of a catalyst system consisting essentially of (I) a titanium containing catalyst component consisting essentially of the solid reaction product obtained by first contacting in an inert solvent (a) an organomagnesium compound, (b) TiCl.sub.4 and thereafter treating with (c) chlorine whereby chlorine is available so that the activity of the catalyst system is increased, and (ii) a co-catalyst comprising an organoaluminum compound represented by the formula AlR".sub.n X'.sub.3-n wherein R" is hydrogen, hydrocarbyl, or a substitute hydrocarbyl group having 1-20 carbon atoms, X' is halogen, and n is 1 to 3; and recovering polymer of higher bulk density than when chlorine is not available.
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