Hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making, method of using, and polyolefins made therewith

Abstract

A Ziegler-Natta type catalyst having an improved hydrogen response provides for narrowing of the MWD of resulting polyolefins polymerized using such catalyst, with such catalyst generally made by a) contacting a soluble magnesium dialkoxide compound of the general formula Mg(OR′) 2 with a halogenating agent capable of exchanging one halogen for one alkoxide to form a reaction product A, where R′ is a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms; b) contacting reaction product A with a first halogenating/titanating agent to form reaction product B; and c) contacting reaction product B with a second halogenating/titanating agent to form a catalyst component; wherein in at least one of steps b) and c), the halogenating/titanating agent is a blend of Ti(OPr) 4 and TiCl 4 . Catalyst components, catalysts, catalyst sytems, polyolefin polymers, and methods of forming each are disclosed.

We claim:  
     
         1 . A catalyst component produced by a process comprising: 
 a) contacting a soluble magnesium dialkoxide compound of the general formula Mg(OR″) 2  with a halogenating agent capable of exchanging one halogen for one alkoxide to form a reaction product A, where R″ is a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms;    b) contacting reaction product A with a first halogenating/titanating agent to form reaction product B; and    c) contacting reaction product B with a second halogenating/titanating agent to form a catalyst component,    wherein the first halogenating/titanating agent is a blend of Ti(OPr) 4 /TiCl 4 .    
     
     
         2 . The catalyst component of  claim 1  wherein the soluble magnesium dialkoxide compound is a reaction product of a reaction comprising an alkyl magnesium compound of the general formula MgRR′, wherein R and R′ are alkyl groups of 1-10 carbon atoms and may be the same or different, and an alcohol of the general formula R″OH wherein the alcohol is linear or branched and wherein R″ is an alkyl group of 4-20 carbon atoms.  
     
     
         3 . The catalyst component of  claim 2  wherein the soluble magnesium compound is a magnesium di(2-ethylhexoxide).  
     
     
         4 . The catalyst component of  claim 2  wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butylethylmagnesium.  
     
     
         5 . The catalyst component of  claim 2  wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.  
     
     
         6 . The catalyst component of  claim 2  wherein the reaction further comprises an aluminum alkyl.  
     
     
         7 . The catalyst component of  claim 6  wherein the aluminum alkyl is triethylaluminum.  
     
     
         8 . The catalyst component of  claim 1  wherein the first halogenating/titanating agent is a blend of Ti(OPr) 4 /TiCl 4  in a ratio of TiCl 4  to Ti(OPr) 4  in the range of about 0.5:1 to about 6:1.  
     
     
         9 . The catalyst component of  claim 1  wherein the reaction further comprises an electron donor.  
     
     
         10 . The catalyst component of  claim 9  wherein the ratio of electron donor to magnesium is in the range of about 0:1 to about 10:1.  
     
     
         11 . The catalyst component of  claim 10  wherein the electron donor is an ether.  
     
     
         12 . The catalyst component of  claim 1  wherein the halogenating agent is of the general formula ClAR′″ x , wherein A is a nonreducing oxyphilic compound, R′″ x  is a hydrocarbyl moiety having from about 2 to 6 carbon atoms, and x is the valence of A minus 1.  
     
     
         13 . A catalyst produced by a process comprising: 
 a) contacting a catalyst component with an organoaluminum preactivating agent, wherein the catalyst component is produced by a process comprising, 
 i) contacting a soluble magnesium dialkoxide compound of the general formula Mg(OR″) 2  with a halogenating agent capable of exchanging one halogen for one alkoxide to form a reaction product A, where R″ is a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms;  
 ii) contacting reaction product A with a first halogenating/titanating agent to form reaction product B; and  
 iii) contacting reaction product B with a second halogenating/titanating agent to form a catalyst component;  
   wherein the first halogenating/titanating agent is a blend of Ti(OPr) 4 /TiCl 4 .    
     
     
         14 . The catalyst of  claim 13  wherein the soluble magnesium dialkoxide compound is a reaction product of a reaction comprising an alkyl magnesium compound of the general formula MgRR′, wherein R and R′ are alkyl groups of 1-10 carbon atoms and may be the same or different, and an alcohol of the general formula R″OH wherein the alcohol is linear or branched and wherein R″ is an alkyl group of 4-20 carbon atoms.  
     
     
         15 . The catalyst of  claim 14  wherein the soluble magnesium compound is a magnesium di(2-ethylhexoxide).  
     
     
         16 . The catalyst of  claim 14  wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butylethylmagnesium.  
     
     
         17 . The catalyst of  claim 14  wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.  
     
     
         18 . The catalyst of  claim 14  wherein the reaction further comprises an aluminum alkyl.  
     
     
         19 . The catalyst of  claim 18  wherein the aluminum alkyl is triethylaluminum.  
     
     
         20 . The catalyst of  claim 13  wherein the first halogenating/titanating agent is a blend of Ti(OPr) 4 /TiCl 4  in a ratio of TiCl 4  to Ti(OPr) 4  in the range of about 0.5:1 to about 6:1.  
     
     
         21 . The catalyst of  claim 14  wherein the reaction further comprises an electron donor.  
     
     
         22 . The catalyst of  claim 21  wherein the ratio of electron donor to magnesium is in the range of about 0:1 to about 10:1.  
     
     
         23 . The catalyst of  claim 22  wherein the electron donor is an ether.  
     
     
         24 . The catalyst of  claim 13  wherein the halogenating agent is of the general formula ClAR′″ x , wherein A is a nonreducing oxyphilic compound, R′″ x  is a hydrocarbyl moiety having from about 2 to 6 carbon atoms, and x is the valence of A minus 1.  
     
     
         25 . The catalyst of  claim 13  wherein the second chlorinating/titanating agent is a titanium halide.  
     
     
         26 . The catalyst of  claim 25  wherein the second chlorinating/titanating agent is titanium tetrachloride, and wherein the range of titanium to magnesium is 0:1 to 2:1.  
     
     
         27 . The catalyst of  claim 13  wherein the organoaluminum preactivating agent is an aluminum alkyl of the formula AlR^  3  where R^ is an alkyl having 1-8 carbon atoms or a halide, R^ being the same or different and at least one R^ is an alkyl.  
     
     
         28 . The catalyst of  claim 25  wherein the organoaluminum preactivating agent is a trialkyl aluminum.  
     
     
         29 . The catalyst of  claim 13  wherein the ratio of aluminum to titanium is in the range from 0.1:1 to 2:1.  
     
     
         30 . The catalyst of  claim 13  wherein the catalyst has a fluff morphology amenable to polymerization production processes, will provide a polyethylene having a molecular weight distribution greater than about 7.0, will have an activity of at least 6,000 gPE/g catalyst, and will provide uniform particle size distributions with low levels of particles of less than about 125 microns.  
     
     
         31 . A polymer produced by a process comprising: 
 a) contacting one or more α-olefin monomers together in the presence of a catalyst under polymerization conditions,    wherein the catalyst was produced by a process comprising 
 i) contacting a soluble magnesium dialkoxide compound of the general formula Mg(OR″) 2  with a halogenating agent capable of exchanging one halogen for one alkoxide to form a reaction product A, where R″ is a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms;  
 ii) contacting reaction product A with a first halogenating/titanating agent to form reaction product B; and  
 iii) contacting reaction product B with a second halogenating/titanating agent to form a catalyst component,  
   wherein the first halogenating/titanating agent is a blend of Ti(OPr) 4 /TiCl 4 .    
     
     
         32 . The polymer of  claim 31  wherein the catalyst is produced by a process further comprising: 
 iv) contacting the catalyst component with an organoaluminum agent.  
 
     
     
         33 . The polymer of  claim 31  wherein the monomers are ethylene monomers.  
     
     
         34 . The polymer of  claim 31  wherein the polymer is polyethylene.  
     
     
         35 . The polymer of  claim 31  wherein the soluble magnesium dialkoxide compound is a reaction product of a reaction comprising an alkyl magnesium compound of the general formula MgRR′, wherein R and R′ are alkyl groups of 1-10 carbon atoms and may be the same or different, and an alcohol of the general formula R″ OH wherein the alcohol is linear or branched and wherein R″ is an alkyl group of 4-20 carbon atoms.  
     
     
         36 . The polymer of  claim 35  wherein the soluble magnesium compound is a magnesium di(2-ethylhexoxide).  
     
     
         37 . The polymer of  claim 35  wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butylethylmagnesium.  
     
     
         38 . The polymer of  claim 35  wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.  
     
     
         39 . The polymer of  claim 35  wherein the reaction further comprises an aluminum alkyl.  
     
     
         40 . The polymer of  claim 39  wherein the aluminum alkyl is triethylaluminum.  
     
     
         41 . The polymer of  claim 31  wherein the first halogenating/titanating agent is a blend of Ti(OPr) 4 /TiCl 4  in a ratio of TiCl 4  to Ti(OPr) 4  in the range of about 0.5:1 to about 6:1.  
     
     
         42 . The polymer of  claim 35  wherein the reaction further comprises an electron donor.  
     
     
         43 . The polymer of  claim 42  wherein the ratio of electron donor to magnesium is in the range of about 0:1 to about 10:1.  
     
     
         44 . The polymer of  claim 43  wherein the electron donor is an ether.  
     
     
         45 . The polymer of  claim 31  wherein the halogenating agent is of the general formula ClAR′″ x , wherein A is a nonreducing oxyphilic compound, R′″ x  is a hydrocarbyl moiety having from about 2 to 6 carbon atoms, and x is the valence of A minus 1.  
     
     
         46 . The polymer of  claim 31  wherein the second chlorinating/titanating agent is a titanium halide.  
     
     
         47 . The polymer of  claim 48  wherein the second chlorinating/titanating agent is titanium tetrachloride, and wherein the range of titanium to magnesium is 0:1 to 2:1.  
     
     
         48 . The polymer of  claim 32  wherein the organoaluminum preactivating agent is an aluminum alkyl of the formula AlR^  3  where R^ is an alkyl having 1-8 carbon atoms or a halide, R^ being the same or different and at least one R^ is an alkyl.  
     
     
         49 . The polymer of  claim 46  wherein the organoaluminum preactivating agent is a trialkyl aluminum.  
     
     
         50 . The polymer of  claim 47  wherein the ratio of aluminum to titanium is in the range from 0.1:1 to 2:1.  
     
     
         51 . A process for forming a catalyst component, the process comprising: 
 a) contacting a soluble magnesium dialkoxide compound of the general formula Mg(OR″) 2  with a halogenating agent capable of exchanging one halogen for one alkoxide to form a reaction product A, where R″ is a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms;    b) contacting reaction product A with a first halogenating/titanating agent to form reaction product B; and    c) contacting reaction product B with a second halogenating/titanating agent to form a catalyst component,    wherein the first halogenating/titanating agent is a blend of Ti(OPr) 4 /TiCl 4 .    
     
     
         52 . The process of  claim 51  wherein the soluble magnesium dialkoxide compound is a reaction product of a reaction comprising an alkyl magnesium compound of the general formula MgRR′, wherein R and R′ are alkyl groups of 1-10 carbon atoms and may be the same or different, and an alcohol of the general formula R″OH wherein the alcohol is linear or branched and wherein R″ is an alkyl group of 4-20 carbon atoms.  
     
     
         53 . The process of  claim 52  wherein the soluble magnesium compound is a magnesium di(2-ethylhexoxide).  
     
     
         54 . The process of  claim 52  wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butylethylmagnesium.  
     
     
         55 . The process of  claim 52  wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.  
     
     
         56 . The process of  claim 52  wherein the reaction further comprises an aluminum alkyl.  
     
     
         57 . The process of  claim 56  wherein the aluminum alkyl is triethylaluminum.  
     
     
         58 . The process of  claim 51  wherein the first halogenating/titanating agent is a blend of Ti(OPr) 4 /TiCl 4  in a ratio of TiCl 4  to Ti(OPr) 4  in the range of about 0.5:1 to about 6:1.  
     
     
         59 . The process of  claim 51  wherein the second chlorinating/titanating agent is a titanium halide.  
     
     
         60 . The process of  claim 59  wherein the second chlorinating/titanating agent is titanium tetrachloride, and wherein the range of titanium to magnesium is 0:1 to 2:1.  
     
     
         61 . A process for making a catalyst, the process comprising: 
 a) contacting a catalyst component with an organoaluminum preactivating agent, wherein the catalyst component is produced by a process comprising 
 i) contacting a soluble magnesium dialkoxide compound of the general formula Mg(OR″) 2  with a halogenating agent capable of exchanging one halogen for one alkoxide to form a reaction product A, where R″ is a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms;  
 ii) contacting reaction product A with a first halogenating/titanating agent to form reaction product B; and  
 iii) contacting reaction product B with a second halogenating/titanating agent, wherein the first halogenating/titanating agent is a blend of Ti(OPr) 4 /TiCl 4 .  
   
     
     
         62 . The process of  claim 61  wherein the first halogenating/titanating agent is a blend of Ti(OPr) 4 /TiCl 4  in a ratio of TiCl 4  to Ti(OPr) 4  in the range of about 0.5:1 to about 6:1.  
     
     
         63 . The process of  claim 62  wherein the ratio of TiCl 4  to Ti(OPr) 4  is about 2:1.  
     
     
         64 . The process of  claim 61  wherein the soluble magnesium dialkoxide compound is a reaction product of a reaction comprising an alkyl magnesium compound of the general formula MgRR′, wherein R and R′ are alkyl groups of 1-10 carbon atoms and may be the same or different, and an alcohol of the general formula R″OH wherein the alcohol is linear or branched and wherein R″ is an alkyl group of 4-20 carbon atoms.  
     
     
         65 . The process of  claim 61  wherein the soluble magnesium compound is a magnesium di(2-ethylhexoxide).  
     
     
         66 . The process of  claim 61  wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butylethylmagnesium.  
     
     
         67 . The process of  claim 61  wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.  
     
     
         68 . The process of  claim 61  wherein the reaction further comprises an aluminum alkyl.  
     
     
         69 . The process of  claim 68  wherein the aluminum alkyl is triethylaluminum.  
     
     
         70 . The process of  claim 61  wherein the reaction further comprises an electron donor.  
     
     
         71 . The process of  claim 70  wherein the ratio of electron donor to magnesium is in the range of about 0:1 to about 10:1.  
     
     
         72 . The process of  claim 71  wherein the electron donor is an ether.  
     
     
         73 . The process of  claim 61  wherein the halogenating agent is of the general formula ClAR′″ x , wherein A is a nonreducing oxyphilic compound, and R′″ x  is a hydrocarbyl moiety having from about 2 to 6 carbon atoms.  
     
     
         74 . The process of  claim 61  wherein the halogenating agent is a blend of TiCl/Ti(O i Pr) 3 .  
     
     
         75 . The process of  claim 61  wherein the second chlorinating/titanating agent is a titanium halide.  
     
     
         76 . The process of  claim 61  wherein the second chlorinating/titanating agent is titanium tetrachloride, and wherein the range of titanium to magnesium is 0:1 to 2:1.  
     
     
         77 . The process of  claim 61  wherein the organoaluminum preactivating agent is an aluminum alkyl.  
     
     
         78 . The process of  claim 61  wherein an electron donor is present in any one of steps a), i), ii), or iii), and wherein the ratio of electron donor to metal is in the range of about 0:1 to about 10:1.  
     
     
         79 . A process for α-olefin polymerization, comprising: 
 a) contacting one or more a-olefin monomers together in the presence of a catalyst under polymerization conditions, wherein the catalyst was produced by a process comprising: 
 i) contacting a soluble magnesium dialkoxide compound of the general formula Mg(OR″) 2  with a halogenating agent capable of exchanging one halogen for one alkoxide to form a reaction product A, where R″ is a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms;  
 ii) contacting reaction product A with a first halogenating/titanating agent to form reaction product B; and  
 iii) contacting reaction product B with a second halogenating/titanating agent to form reaction product C,  
 
 wherein the first halogenating/titanating agent is a blend of Ti(OPr) 4 /TiCl 4 .  
 
     
     
         80 . The process of  claim 79  further comprising: 
 b) extracting a polyolefin polymer.  
 
     
     
         81 . The process of  claim 80  wherein the polymer has a molecular weight distribution of less than about 7.0.  
     
     
         82 . The process of  claim 80  wherein the polymer is a polyethylene.  
     
     
         83 . The process of  claim 79  wherein the catalyst is produced by a process further comprising: 
 iv) contacting reaction product C with an organoaluminum agent.  
 
     
     
         84 . The process of  claim 79  wherein the first halogenating/titanating agent is a blend of Ti(OPr) 4 /TiCl 4  in a ratio of TiCl 4  to Ti(OPr) 4  in the range of about 0.5:1 to about 6:1.  
     
     
         85 . The process of  claim 84  wherein the ratio of TiCl 4  to Ti(OPr) 4  is about 2:1.  
     
     
         86 . The process of  claim 79  wherein the halogenating agent of step i) is of the general formula ClAR′″ x , wherein A is a nonreducing oxyphilic compound, and R′″ x  is a hydrocarbyl moiety having from about 2 to 6 carbon atoms.  
     
     
         87 . The process of  claim 86  wherein the halogenating agent is ClTi(O 1 Pr) 3 .  
     
     
         88 . The process of  claim 86  wherein the second chlorinating/titanating agent is a titanium halide.  
     
     
         89 . The process of  claim 88  wherein the second chlorinating/titanating agent is titanium tetrachloride, and wherein the range of titanium to magnesium is 0:1 to 2:1.  
     
     
         90 . The process of  claim 79  wherein the organoaluminum agent is triethylaluminum.  
     
     
         91 . The process of  claim 79  wherein an electron donor is present in any one of steps i)-iv), and wherein the ratio of electron donor to metal is in the range of about 0:1 to about 10:1.