US2003229186A1PendingUtilityA1

Polymerization process

46
Priority: Dec 4, 2000Filed: Jun 11, 2003Published: Dec 11, 2003
Est. expiryDec 4, 2020(expired)· nominal 20-yr term from priority
Inventors:Simon MawsonSun-Chueh KaoTae Hoon KwalkTimothy R. LynnDavid H. McconvilleMatthew MckeeJohn F. SzulKersten Anne TerryTimothy T. WenzelMark G. GoodeJohn H. OskamRobert J. JorgensenRobert Harold Vogel
C08F 10/00C08F 4/65912C08F 210/16C08F 4/65925Y10S526/943Y10S526/905C08F 4/659
46
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Claims

Abstract

The invention provides for polymerization catalyst compositions, and for methods for introducing the catalyst compositions into a polymerization reactor. More particularly, the method combines a catalyst component containing slurry and a catalyst component containing solution to form the completed catalyst composition for introduction into the polymerization reactor. The invention is also directed to methods of preparing the catalyst component slurry, the catalyst component solution and the catalyst compositions, to methods of controlling the properties of polymer products utilizing the catalyst compositions, and to polymers produced therefrom.

Claims

exact text as granted — not AI-modified
We claim:  
     
         1 . A polymer product produced by a method comprising: 
 a) continuously combining a catalyst component slurry with a catalyst component solution to form a catalyst composition;    b) combining the catalyst composition with one or more olefin(s) in a polymerization reactor to form a polymer product;    c) measuring a sample of the polymer product to obtain an initial product property;    d) changing a process parameter to obtain a second product property; and    e) isolating a polymer product.    
     
     
         2 . The polymer product of  claim 1 , wherein the catalyst component slurry comprises a first catalyst compound and the catalyst component solution comprises a second catalyst compound.  
     
     
         3 . The polymer product of  claim 2 , wherein the molar ratio of the first catalyst compound to the second catalyst compound in the catalyst composition is between about 500:1 to about 1:500.  
     
     
         4 . The polymer product of  claim 1 , wherein the product property is selected form the group consisting of flow index, melt index, density, MWD, comonomer content, and combinations thereof.  
     
     
         5 . The polymer product of  claim 1 , wherein step d) is selected from the group consisting of changing a hydrogen concentration, changing a first catalyst amount, changing a second catalyst amount, changing an amount of a liquid and/or a gas that is withdrawn from the reactor, changing a polymerization temperature, changing an olefin(s) partial pressure, changing an olefin to comonomer ratio, changing an activator to a transition metal ratio, changing a relative feed rates of the catalyst component slurry and/or the catalyst component solution; changing a time or a degree of or a temperature of the combining of the catalyst component slurry and the catalyst component solution and combinations thereof.  
     
     
         6 . The polymer product of  claim 3 , wherein product property is flow index and wherein the process parameter is selected from the group consisting of temperature, catalyst compound feed rate, a molar ratio of the first and second catalyst compound, monomer partial pressure, oxygen concentration, hydrogen concentration, and a combination thereof.  
     
     
         7 . The polymer product of  claim 6 , wherein the sample of polymer product are melt-homogenized before the flow index is measured.  
     
     
         8 . The polymer product of  claim 1  wherein the process parameter is monomer partial pressure.  
     
     
         9 . The polymer product of  claim 2 , wherein the first catalyst compound is a Group 15 containing metal compound and where in the second catalyst compound is a metallocene compound.  
     
     
         10 . The polymer product of  claim 1 , wherein the polymer product is a multimodal or bimodal polyethylene comprising a high molecular weight fraction and a low molecular weigh fraction; the polymer product having a density of from 0.930 g/cc to 0.965 g/cc and a Mw/Mn of from 20 to 50.  
     
     
         11 . The polymer product of  claim 1 , wherein the polymer product is separated into fractions according to the following table:  
       
         
           
                 
                 
                 
               
                     
                 
                     
                 
                   Sieve size 
                   Fraction Collected 
                   Fraction Name 
                 
                     
                 
                   10 mesh 
                   >2000 μm 
                   Fraction 1 
                 
                   18 mesh 
                   2000−1000 μm 
                   Fraction 2 
                 
                   35 mesh 
                   <1000−500 μm 
                   Fraction 3 
                 
                   60 mesh 
                   <500−250 μm 
                   Fraction 4 
                 
                   120 mesh 
                   <250−125 μm 
                   Fraction 5 
                 
                   200 mesh/Pan 
                   <125 μm 
                   Fraction 6 
                 
                     
                 
                     
                 
             
                
                
                
                
               
               
                
                
                
                
                
                
                
                
               
            
           
         
       
       and the melt indices of Fractions 3, 4 and 5 do not vary by more than 30% relative to each other.  
     
     
         12 . A film, pipe or blow molded product comprising the polymer of  claim 1 .  
     
     
         13 . A polymer product produced by a method comprising: 
 a) continuously combining a catalyst component slurry with a catalyst component solution to form a catalyst composition;    b) combining the catalyst composition with one or more olefin(s) in a polymerization reactor to form a polymer product; and    c) isolating a polymer product.    
     
     
         14 . The polymer product of  claim 13 , wherein the catalyst component slurry comprises a first catalyst compound and the catalyst component solution comprises a second catalyst compound.  
     
     
         15 . The polymer product of  claim 14 , wherein the molar ratio of the first catalyst compound to the second catalyst compound in the catalyst composition is between about 500:1 to about 1:500.  
     
     
         16 . The polymer product of  claim 14 , wherein the first catalyst compound is a Group 15 containing metal compound and where in the second catalyst compound is a metallocene compound.  
     
     
         17 . The polymer product of  claim 13 , wherein the polymer product is a multimodal or bimodal polyethylene comprising a high molecular weight fraction and a low molecular weigh fraction; the polymer product having a density of from 0.930 g/cc to 0.965 g/cc and a Mw/Mn of from 20 to 50.  
     
     
         18 . The polymer product of  claim 13 , wherein the polymer product is a multimodal or bimodal polyethylene comprising a high molecular weight fraction and a low molecular weigh fraction in a weight percent ratio of from 30-70 to 70-30; the polymer product having a I 21 /I 2  of greater than 50 and a density of from 0.930 g/cc to 0.965 g/cc.  
     
     
         19 . The polymer product of  claim 13 , wherein the polymer product is a multimodal or bimodal polyethylene comprising a high molecular weight fraction and a low molecular weigh fraction; wherein the low molecular weight fraction has a density of 0.935 to 0.975 g/cc and the high molecular weight fraction has a density of 0.910 to 0.950 g/cc.  
     
     
         20 . The polymer product of  claim 13 , wherein the catalyst component slurry further comprises an alumoxane supported on an inorganic oxide.  
     
     
         21 . A bimodal polymer product produced by a method comprising: 
 a) continuously combining a catalyst component slurry with a catalyst component solution to form a catalyst composition;    b) combining the catalyst composition with one or more olefin(s) in a gas phase polymerization reactor to form a polymer product; and    c) isolating a bimodal polymer product;    wherein the catalyst component slurry comprises a support, an alumoxane, a metallocene catalyst compound and a Group 15 containing catalyst compound represented by the formulae:                          wherein 
 M is a Group 4, 5, or 6 metal;  
 each X is independently a leaving group;  
 y is 0 or 1, wherein when y is 0, group L′ is absent;  
 n is the oxidation state of M;  
 m is the formal charge of the ligand represented by YZL and YZL′;  
 L, L′, Y and Z are each a Group 15 element;  
 R 1  and R 2  are independently a C 1  to C 20  hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, halogen or phosphorus;  
 R 3  is absent or a hydrocarbon group, hydrogen, a halogen, a heteroatom containing group;  
 R 4  and R 5  are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkyl group, a substituted cyclic arylalkyl group or multiple ring system;  
 R 6  and R 7  are independently absent, or hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group; and  
 R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.  
   
     
     
         21 . The bimodal polymer product of  claim 20 , wherein the metallocene catalyst compound is selected from the group consisting of unbridged zirconocenes, unbridged hafnocenes, bridged zirconocenes and bridged hafnocenes.  
     
     
         22 . The bimodal polymer product of  claim 20 , wherein the support is a fumed silica.  
     
     
         23 . The bimodal polymer product of  claim 20 , wherein the catalyst component solution comprises a metallocene.  
     
     
         24 . The bimodal polymer product of  claim 20 , wherein the catalyst component slurry comprises mineral oil.  
     
     
         25 . The bimodal polymer product of  claim 20 , wherein the polymer product is a multimodal or bimodal polyethylene comprising a high molecular weight fraction and a low molecular weigh fraction; the polymer product having a density of from 0.930 g/cc to 0.965 g/cc and a Mw/Mn of from 20 to 50.  
     
     
         26 . The bimodal polymer product of  claim 20 , wherein the polymer product is a multimodal or bimodal polyethylene comprising a high molecular weight fraction and a low molecular weigh fraction in a weight percent ratio of from 30-70 to 70-30; the polymer product having a I 21 /I 2  of greater than 50 and a density of from 0.930 g/cc to 0.965 g/cc.  
     
     
         27 . The bimodal polymer product of  claim 20 , wherein the polymer product is a multimodal or bimodal polyethylene comprising a high molecular weight fraction and a low molecular weigh fraction; wherein the low molecular weight fraction has a density of 0.935 to 0.975 g/cc and the high molecular weight fraction has a density of 0.910 to 0.950 g/cc.  
     
     
         28 . A pipe or blow molded product comprising the polymer of any of claims  25 ,  26  or  27 .  
     
     
         29 . A bimodal polymer comprising a high molecular weight fraction and a low molecular weigh fraction in a weight percent ratio of from 20-80 to 80-20; the polymer product having a I 21 /I 2  of greater than 30 and a density of from 0.930 g/cc to 0.965 g/cc; the bimodal polymer produced by combining C 2  to C 8  olefins with a catalyst composition comprising a Group 15 containing catalyst compound represented by the formulae:  
       
         
           
           
               
               
           
         
       
       wherein 
 M is a Group 4, 5, or 6 metal;  
 each X is independently a leaving group;  
 y is 0 or 1, wherein when y is 0, group L′ is absent;  
 n is the oxidation state of M;  
 m is the formal charge of the ligand represented by YZL and YZL′;  
 L, L′, Y and Z are each a Group 15 element;  
 R 1  and R 2  are independently a C 1  to C 20  hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, halogen or phosphorus;  
 R 3  is absent or a hydrocarbon group, hydrogen, a halogen, a heteroatom containing group;  
 R 4  and R 5  are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkyl group, a substituted cyclic arylalkyl group or multiple ring system;  
 R 6  and R 7  are independently absent, or hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group; and  
 R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.  
 
     
     
         30 . The bimodal polymer of  claim 29 , wherein the Group 15 containing compound is represented by Formula I; and wherein R 1  and R 2  are a C 2  to C 6  hydrocarbon group and R 3  is hydrogen.  
     
     
         31 . The bimodal polymer of  claim 30 , wherein M is zirconium or hafnium.  
     
     
         32 . The bimodal polymer of  claim 31 , wherein L, Y and Z are each nitrogen; and R 6  and R 7  are absent.  
     
     
         33 . The bimodal polymer of  claim 32 , wherein R 4  and R 5  are each a substituted aryl group.  
     
     
         34 . The bimodal polymer of  claim 29 , wherein the catalyst composition further comprises an alumoxane and an inorganic oxide support.  
     
     
         35 . The bimodal polymer of  claim 29 , wherein the catalyst composition further comprises a metallocene compound.  
     
     
         36 . The bimodal polymer of  claim 29 , wherein the catalyst composition further comprises mineral oil.  
     
     
         37 . The bimodal polymer of  claim 29 , wherein the weight percent fraction of high molecular weight fraction to low molecular weight fraction is from 30-70 to 70-30; and the bimodal polymer has an I 21 /I 2  of greater than 50 and a density of from 0.930 g/cc to 0.965 g/cc and a Mw/Mn of from 20 to 50.  
     
     
         38 . The bimodal polymer of  claim 29 , wherein the polymer has an I 21  value of from 4 to 13 g/10 min and an I 2  of from 0.03 to 0.1 g/10 min.  
     
     
         39 . A pipe or blow molded product comprising the polymer of  claim 29.

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