Cyclobutyl silanes for catalysts useful for making highly isotactic olefin polymers

Abstract

One aspect of the present invention relates to a catalyst system for use in olefinic polymerization, containing a solid titanium catalyst component prepared by contacting a titanium compound and a magnesium compound; an organoaluminum compound having at least one aluminum-carbon bond; and an organosilicon compound comprising at least one of cyclobutyl group. Another aspect of the present invention relates to a method of making a catalyst for use in olefinic polymerization, involving the steps of reacting a Grignard reagent having a cyclobutyl group with an orthosilicate to provide an organosilicon compound having a cyclobutyl moiety; and combining the organosilicon compound with an organoaluminum compound having at least one aluminum-carbon bond and a solid titanium catalyst component prepared by contacting a titanium compound and a magnesium compound.

What is claimed is:  
     
       1. A catalyst system for use in olefinic polymerization, comprising: 
       a solid titanium catalyst component prepared by contacting a titanium compound and a magnesium compound;  
       an organoaluminum compound having at least one aluminum-carbon bond; and  
       an organosilicon compound comprising at least one of dicyclobutyl dimethoxysilane, (cyclobutyl)methyl cyclobutyl dimethoxysilane, (cyclopropyl)methyl cyclobutyl dimethoxysilane, cyclobutylcyclopropyl dimethoxysilane, cyclobutyl methyl dimethoxysilane, cyclobutyl ethyl dimethoxysilane, cyclobutyl isopropyl dimethoxysilane, cyclobutyl butyl dimethoxysilane, cyclobutyl cyclopropyl dimethoxysilane, cyclobutyl cyclopentyl dimethoxysilane, cyclobutyl cyclohexyl dimethoxysilane, cyclobutyl 2-ethylhexyl dimethoxysilane, dimethylcyclobutyl dimethoxysilane, di-2-methylcyclobutyl dimethoxysilane, di-t-butylcyclobutyl dimethoxysilane, di-2-t-tbutylcyclobutyl dimethoxysilane, cyclobutyl trimethoxysilane, dicyclobutyl diethoxysilane, (cyclobutyl)methyl cyclobutyl diethoxysilane, (cyclopropyl)methyl cyclobutyl diethoxysilane, cyclobutylcyclopropyl diethoxysilane, cyclobutyl methyl diethoxysilane, cyclobutyl ethyl diethoxysilane, cyclobutyl isopropyl diethoxysilane, cyclobutyl butyl diethoxysilane, cyclobutyl cyclopropyl diethoxysilane, cyclobutyl cyclopentyl diethoxysilane, cyclobutyl cyclohexyl diethoxysilane, cyclobutyl 2-ethylhexyl diethoxysilane, dimethylcyclobutyl diethoxysilane, di-2-methylcyclobutyl diethoxysilane, di-t-butylcyclobutyl diethoxysilane, di-2-t-tbutylcyclobutyl diethoxysilane, and cyclobutyl triethoxysilane.  
     
     
       2. The catalyst system according to  claim 1 , wherein the solid titanium catalyst component is prepared by contacting the titanium compound and the magnesium compound in the presence of at least one of an internal electron donor, an organic epoxy compound, and an organic phosphorus compound. 
     
     
       3. The catalyst system according to  claim 1 , wherein the titanium compound comprises at least one of titanium tetrahalides, alkoxytitanium trihalides, dialkoxytitanium dihalides, trialkoxytitanium monohalides, and tetraalkoxytitaniums. 
     
     
       4. The catalyst system according to  claim 1 , wherein the magnesium compound comprises at least one of ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butylethoxymagnesium, magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, phenoxy magnesium chloride, methylphenoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium, phenoxy magnesium, dimethylphenoxy magnesium, magnesium laurate and magnesium stearate. 
     
     
       5. The catalyst system according to  claim 1 , wherein the organoaluminum compound comprises at least one of triethyl aluminum, tributyl aluminum, triisoprenyl aluminum, diethyl aluminum ethoxide, dibutyl aluminum butoxide, ethyl aluminum sesquiethoxide, butyl aluminum sesquibutoxide, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, diethyl aluminum hydride, dibutyl aluminum hydride, ethyl aluminum dihydride, propyl aluminum dihydride, ethyl aluminum ethoxychloride, butyl aluminum butoxychloride, ethyl aluminum ethoxybromide, (C 2 H 5 ) 2 AlOAl(C 2 H 5 ) 2 , (C 4 H,) 2 AlOAl(C 4 H 9 ) 2 , methylaluminoxane, LiAl(C 2 H 5 ) 4  and LiAl(C 7 H 15 ) 4 . 
     
     
       6. The catalyst system according to  claim 1 , wherein the catalyst system comprises from about 0.001 to about 0.75 millimole of the solid titanium catalyst component, from about 1 to about 2,000 moles of the organoaluminum compound per mole of titanium atoms in the solid titanium catalyst component, and from about 0.001 to about 10 moles of the organosilicon compound. 
     
     
       7. The catalyst system according to  claim 1 , wherein the organosilicon compound comprises at least one of dicyclobutyl dimethoxysilane, cyclobutyl cyclopentyl dimethoxysilane, cyclobutyl cyclohexyl dimethoxysilane, and cyclobutyl 2-ethylhexyl dimethoxysilane. 
     
     
       8. A catalyst system for use in olefinic polymerization, comprising: 
       a solid titanium catalyst component prepared by contacting a titanium compound and a magnesium compound, the solid titanium catalyst component comprising from about 0.01 to about 500 moles of the titanium compound per mole of the magnesium compound;  
       an organoaluminum compound having at least one aluminum-carbon bond, wherein the catalyst has a mole ratio of aluminum to titanium from about 5 to about 1,000; and  
       an organosilicon compound comprising at least one of dicyclobutyl dimethoxysilane, (cyclobutyl)methyl cyclobutyl dimethoxysilane, (cyclopropyl)methyl cyclobutyl dimethoxysilane, cyclobutylcyclopropyl dimethoxysilane, cyclobutyl methyl dimethoxysilane, cyclobutyl ethyl dimethoxysilane, cyclobutyl isopropyl dimethoxysilane, cyclobutyl butyl dimethoxysilane, cyclobutyl cyclopropyl dimethoxysilane, cyclobutyl cyclopentyl dimethoxysilane, cyclobutyl cyclohexyl dimethoxysilane, cyclobutyl 2-ethylhexyl dimethoxysilane, dimethylcyclobutyl dimethoxysilane, di-2-methylcyclobutyl dimethoxysilane, di-t-butylcyclobutyl dimethoxysilane, di-2-t-tbutylcyclobutyl dimethoxysilane, cyclobutyl trimethoxysilane, dicyclobutyl diethoxysilane, (cyclobutyl)methyl cyclobutyl diethoxysilane, (cyclopropyl)methyl cyclobutyl diethoxysilane, cyclobutylcyclopropyl diethoxysilane, cyclobutyl methyl diethoxysilane, cyclobutyl ethyl diethoxysilane, cyclobutyl isopropyl diethoxysilane, cyclobutyl butyl diethoxysilane, cyclobutyl cyclopropyl diethoxysilane, cyclobutyl cyclopentyl diethoxysilane, cyclobutyl cyclohexyl diethoxysilane, cyclobutyl 2-ethylhexyl diethoxysilane, dimethylcyclobutyl diethoxysilane, di-2-methylcyclobutyl diethoxysilane, di-t-butylcyclobutyl diethoxysilane, di-2-t-tbutylcyclobutyl diethoxysilane, and cyclobutyl triethoxysilane, wherein the catalyst system has a mole ratio of the organoaluminum compound to the organosilicon compound from about 2 to about 90.  
     
     
       9. A method of making a catalyst for use in olefinic polymerization, comprising: 
       reacting a Grignard reagent having a cyclobutyl group with an orthosilicate to provide an organosilicon compound having a cyclobutyl moiety; and  
       combining the organosilicon compound with an organoaluminum compound having at least one aluminum-carbon bond and a solid titanium catalyst component prepared by contacting a titanium compound and a magnesium compound.  
     
     
       10. The method of  claim 9  further comprising purifying the organosilicon compound by vacuum distillation. 
     
     
       11. The method of  claim 9 , wherein the orthosilicate is tetramethylorthosilicate or tetraethylorthosilicate. 
     
     
       12. The method of  claim 9 , wherein the Grignard reagent comprises a compound represented by Formula (IX) 
       
         
           MgXR 13    (IX)  
         
       
       wherein X is a halogen atom, and R 13  is an organic group containing a cyclobutyl group. 
     
     
       13. The method of  claim 9 , wherein the organosilicon compound comprises at least one of dicyclobutyl dimethoxysilane, (cyclobutyl)methyl cyclobutyl dimethoxysilane, (cyclopropyl)methyl cyclobutyl dimethoxysilane, cyclobutylcyclopropyl dimethoxysilane, cyclobutyl methyl dimethoxysilane, cyclobutyl ethyl dimethoxysilane, cyclobutyl isopropyl dimethoxysilane, cyclobutyl butyl dimethoxysilane, cyclobutyl cyclopropyl dimethoxysilane, cyclobutyl cyclopentyl dimethoxysilane, cyclobutyl cyclohexyl dimethoxysilane, cyclobutyl 2-ethylhexyl dimethoxysilane, dimethylcyclobutyl dimethoxysilane, di-2-methylcyclobut yl dimethoxysilane, di-t-butylcyclobutyl dimethoxysilane, di-2-t-tbutylcyclobutyl dimethoxysilane, cyclobutyl trimethoxysilane, dicyclobutyl diethoxysilane, (cyclobutyl)methyl cyclobutyl diethoxysilane, (cyclopropyl)methyl cyclobutyl diethoxysilane, cyclobutylcyclopropyl diethoxysilane, cyclobutyl methyl diethoxysilane, cyclobutyl ethyl diethoxysilane, cyclobutyl isopropyl diethoxysilane, cyclobutyl butyl diethoxysilane, cyclobutyl cyclopropyl diethoxysilane, cyclobutyl cyclopentyl diethoxysilane, cyclobutyl cyclohexyl diethoxysilane, cyclobutyl 2-ethylhexyl diethoxysilane, dimethylcyclobutyl diethoxysilane, di-2-methylcyclobutyl diethoxysilane, di-t-butylcyclobutyl diethoxysilane, di-2-t-tbutylcyclobutyl diethoxysilane, and cyclobutyl triethoxysilane. 
     
     
       14. A polymerization process, comprising: 
       polymerizing or copolymerizing an alpha-olefin in the presence of a catalyst system comprising:  
       a solid titanium catalyst component prepared by contacting a titanium compound and a magnesium compound;  
       an organoaluminum compound having at least one aluminum-carbon bond; and  
       an organosilicon compound comprising at least one of dicyclobutyl dimethoxysilane, (cyclobutyl)methyl cyclobutyl dimethoxysilane, (cyclopropyl)methyl cyclobutyl dimethoxysilane, cyclobutylcyclopropyl dimethoxysilane, cyclobutyl methyl dimethoxysilane cyclobutyl ethyl dimethoxysilane, cyclobutyl isopropyl dimethoxysilane, cyclobutyl butyl dimethoxysilane, cyclobutyl cyclopropyl dimethoxysilane, cyclobutyl cyclopentyl dimethoxysilane, cyclobutyl cyclohexyl dimethoxysilane, cyclobutyl 2-ethylhexyl dimethoxysilane, dimethylcyclobutyl dimethoxysilane, di-2-methylcyclobutyl dimethoxysilane, di-t-butylcyclobutyl dimethoxysilane, di-2-tbutylcyclobutyl dimethoxysilane, cyclobutyl trimethoxysilane, dicyclobutyl diethoxysilane, (cyclobutyl)methyl cyclobutyl diethoxysilane, (cyclopropyl)methyl cyclobutyl diethoxysilane, cyclobutylcyclopropyl diethoxysilane, cyclobutyl methyl diethoxysilane, cyclobutyl ethyl diethoxysilane, cyclobutyl isopropyl diethoxysilane, cyclobutyl butyl diethoxysilane, cyclobutyl cyclopropyl diethoxysilane, cyclobutyl cyclopentyl diethoxysilane, cyclobutyl cyclohexyl diethoxysilane, cyclobutyl 2-ethylhexyl diethoxysilane, dimethylcyclobutyl diethoxysilane, di-2-methylcyclobutyl diethoxysilane, di-t-butylcyclobutyl diethoxysilane, di-2-t-tbutylcyclobutyl diethoxysilane, and cyclobutyl triethoxysilane.  
     
     
       15. The polymerization process of  claim 14 , wherein during polymerization a temperature from about 20° C. to about 200° C. and a pressure from about atmospheric pressure to about 100 kg/cm 2  is maintained. 
     
     
       16. The polymerization process of  claim 14 , wherein the organosilicon compound comprises at least one of dicyclobutyl dimethoxysilane, cyclobutyl cyclopentyl dimethoxysilane, cyclobutyl cyclohexyl dimethoxysilane, and cyclobutyl 2-ethylhexyl dimethoxysilane. 
     
     
       17. The polymerization process of  claim 14 , wherein the catalyst system has a catalyst efficiency of at least about 25 kg of polymer produced/g catalyst. 
     
     
       18. The polymerization process of  claim 14 , wherein the alpha-olefin comprises at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-hexene, 3-methyl-i-pentene, 3-methyl-i-butene, 1-decene, 1-tetradecene, 1-eicosene, and vinylcyclohexane. 
     
     
       19. The polymerization process of  claim 14 , wherein the alpha-olefin comprises at least two of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-hexene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-decene, 1-tetradecene, 1-eicosene, and vinylcyclohexane. 
     
     
       20. The polymerization process of  claim 14 , wherein at least one of styrene, butadiene, acrylonitrile, acrylamide, alpha-methyl styrene, chlorostyrene, vinyl toluene, divinyl benzene, diallylphthalate, alkyl methacrylates and alkyl acrylates is copolymerized with the alpha-olefin.