Process for the preparation of high performance polypropylene

Abstract

The invention discloses a process for preparing high-performance propylene polymers, the process utilizing a high activity, highly stereoselective Ziegler-Natta catalyst and two or more stages of polymerization carried out under different hydrogen concentrations to prepare propylene polymers having broad molecular weight distribution, wherein non-unifomess of isotacticity of molecular chains of the final propylene polymers is improved by adjusting or controlling stereoselectivity of catalytic active sites under different hydrogen concentrations, namely, making the low molecular weight fraction of the polymers having a higher isotacticity and making the high molecular weight fraction of the polymers having a lower isotacticity, thereby overcoming the drawbacks of the propylene polymers having broad molecular weight distribution known in the art. The resulting final polymers have excellent combined properties, in particular, remarkably improved mechanical properties.

1 . A process for preparing a polypropylene having broad molecular weight distribution, the process comprising at least the following two stages of polymerization: a first stage of polymerization, which is homopolymerization of propylene or copolymerization of propylene and an α-olefin carried out in the presence of a Ziegler-Natta catalyst and a less amount of a molecular weight control agent, to provide a high molecular weight fraction of the polypropylene; and a second stage of polymerization, which is homopolymerization of propylene or copolymerization of propylene and an α-olefin carried out in the presence of the resulting polymer from the first stage of polymerization and a larger amount of the molecular weight control agent, to provide a low molecular weight fraction of the polypropylene, wherein the first stage of polymerization employs optionally an external electron donor compound, and the second stage of polymerization employs an external electron donor compound, wherein the amount and/or kind of the external electron donor compound used in the second stage of polymerization are/is selected so as to give a final polymer having an isotacticity higher than that of the polymer produced in the first stage of polymerization, and wherein a ratio of the output of the first stage of polymerization to the output of the second stage of polymerization is in a range of from 30:70 to 70:30. 
   
   
       2 . The process according to  claim 1 , wherein a ratio of the MFR value of the final polymer to the MFR value of the propylene polymer prepared in the first stage of polymerization is in a range of from 5 to 15. 
   
   
       3 . The process according to  claim 1 , wherein a ratio of the isotacticity of the final polymer to the isotacticity of the propylene polymer prepared in the first stage of polymerization is larger than 1 but less than or equal to 1.2. 
   
   
       4 . The process according to  claim 1 , wherein the Ziegler-Natta catalyst used in the first stage of polymerization is a reaction product of: a solid catalyst component comprising magnesium, titanium, a halogen and an internal electron donor as essential components, an organic aluminum compound, and an organic silicon compound, with a weight ratio of the organic aluminum compound to the organic silicon compound being in a range of from 10 to 300, and wherein an additional amount of the organic silicon compound is added in the second stage of polymerization so as to give a weight ratio of the organic aluminum compound to the organic silicon compound less than that in the first stage of polymerization. 
   
   
       5 . The process according to  claim 4 , wherein the weight ratio of the organic aluminum compound to the organic silicon compound in the first stage of polymerization is 2 to 20 times larger than that in the second stage of polymerization. 
   
   
       6 . The process according to  claim 1 , wherein the process comprises the first and second stages of polymerization, and the first and second stages of polymerization are carried out in a first loop reactor and a second loop reactor in series, respectively. 
   
   
       7 . The process according to  claim 6 , wherein the ratio of the output of the first stage of polymerization to the output of the second stage of polymerization is in a range of from about 35:65 to about 55:45, polymerization temperatures in the two loop reactors are controlled at 60 to 80° C., and the polymerization is conducted in a liquid phase bulk process. 
   
   
       8 . A process for preparing a polypropylene having broad molecular weight distribution, the process comprising successively performing homopolymerization or copolymerization of propylene in two loop reactors in series in the presence of a highly-stereoselective Ziegler-Natta catalyst, which comprise a reaction product of an active titanium-containing solid catalyst component, an organic aluminum compound and an organic silicon compound, wherein in the first loop reactor, a weight ratio of the organic aluminum compound to the organic silicon compound is in a range of from 10 to 300; an additional amount of the organic silicon compound is added in the second loop reactor so that a weight ratio of the organic aluminum compound to the organic silicon compound in the second loop reactor is less than that in the first loop reactor; a concentration of a molecular weight control agent in the second loop reactor is larger than that in the first loop reactor; a ratio of the output of the first loop reactor to the output of the second loop reactor is in a range of from about 35:65 to about 55:45; polymerization temperatures in the two loop reactors are controlled at 60 to 80° C.; and the polymerization is a liquid phase bulk polymerization. 
   
   
       9 . The process according to  claim 8 , wherein the weight ratio of the organic aluminum compound to the organic silicon compound in the first loop reactor is 2 to 20 times larger than that in the second loop reactor. 
   
   
       10 . A polypropylene preparable by the process as claimed in  claim 1 . 
   
   
       11 . A polypropylene preparable by the process as claimed in  claim 8 . 
   
   
       12 . A polypropylene, which has a polydispersity index of 3 to 10, and of which the isotacticity of the low molecular weight fraction is higher than the isotacticity of the high molecular weight fraction. 
   
   
       13 . Biaxial oriented films, tubings, flat fibers, or injection mould articles prepared from the polypropylene as claimed in  claim 10 . 
   
   
       14 . Biaxial oriented films, tubings, flat fibers, or injection mould articles prepared from the polypropylene as claimed in  claim 11 . 
   
   
       15 . Biaxial oriented films, tubings, flat fibers, or injection mould articles prepared from the polypropylene as claimed in  claim 12 .