Propylene random copolymer

Abstract

Propylene random copolymers with low randomness and being free of from catalyst originating phthalates.

1 . Propylene random copolymers comprising,
 a) a comonomer selected from ethylene, C 4 -C 20 -alpha olefin, and any combination thereof   b) a comonomer content in the range of 1.5 to at most 5.0 wt %   c) a randomness in the range of 60% to at most 80%   d) a xylene soluble (XS) content of 2 to <12 wt %,   the propylene random copolymers being free of from catalyst originating phthalates.   
     
     
         2 . Propylene random copolymers according to  claim 1 , wherein
 a) the comonomer is ethylene   b) the comonomer content is in the range of 2.0 to 4.9 wt %   c) the randomness is in the range of 65% to 80%   d) a xylene soluble (XS) content of 3.0 to <11.5 wt %,   the propylene random copolymers being free of from catalyst originating phthalates.   
     
     
         3 . Process for preparing propylene random copolymers according to  claim 1 , said propylene random copolymers being produced by copolymerising propylene with a comonomer selected from ethylene, C 4 -C 20 -alpha olefin, and any combination thereof using a catalyst system comprising a co-catalyst and optionally an external electron donor and an olefin polymerisation catalyst component in the form of solid particles being produced by
 a) preparing a solution of at least one alkoxy compound (Ax) being the reaction product of at least one compound of a Group 2 metal with at least a monohydric alcohol (A) in an organic liquid reaction medium,   b) adding said solution to at least one compound of a transition metal and   c) preparing the solid catalyst component particles,   wherein an internal electron donor selected from benzoates, alkylene glycol dibenzoates, maleates, 1-cyclohexene-1,2-dicarboxylic dialkylester, and 1,3-ethers, or a mixture of any selected donors, or a corresponding precursor is added at any step prior to step c).   
     
     
         4 . Process according to  claim 3 , wherein the internal donors are selected from
 a) benzoates of the formula (I)   
       
         
           
           
               
               
           
         
         
           with R being a linear or branched C 1 -C 12 -alkyl group, preferably a linear or branched C 2 -C 10 -alkyl group, more preferably a linear or branched C 4 -C 9 -alkyl group and most preferably a branched C 6 -C 8 -alkyl group and R′ being H or a linear or branched C 1 -C 12 -alkyl group, preferably a linear or branched C 2 -C 10 -alkyl group more preferably a linear or branched C 4 -C 8 -alkyl group, whereby the alkyl group can contain one or more heteroatoms selected from O, N or S, preferably O or N, more preferably O, in the alkyl chain, or can be substituted by one or more substituents selected from ═O, halogen, like chlorine, fluorine or bromine, or optionally substituted C 6 -C 14 -aryl, 
         
         b) alkylene glycol dibenzoates of the formula (II) 
       
       
         
           
           
               
               
           
         
         
           with n being 1 or 2, if n=1 then R═CH 3  and if n=2 then R═H, 
         
         c) maleates of formula (III) 
       
       
         
           
           
               
               
           
         
         
           with R 1  and R 2  being the same or different and being a linear or branched C 1 -C 12 -alkyl group, preferably a linear or branched C 1 -C 8 -alkyl group, more preferably a linear or branched C 1 -C 4 -alkyl group and most preferably ethyl, whereby R 1  and R 2  are preferably the same and 
           with R being H or a linear, branched or cyclic C 1  to C 12 -alkyl, preferably a branched or cyclic C 3  to C 8 -alkyl, 
         
         d) 1-cyclohexene-1,2-dicarboxylic dialkylester of formula (IV) 
       
       
         
           
           
               
               
           
         
         
           with R 1  and R 2  can be identical or different and can be a linear or branched C 5 -C 20 -alkyl, and 
         
         e) 1,3-diethers of formula (V) or (VI) 
       
       
         
           
           
               
               
           
         
         
           wherein in formula (V) and (VI) 
           R 1  and R 2  are the same or different and can be a linear or branched C 1 -C 12 -alkyl, or R 1  with R 5  and/or R 2  with R 6  can form a ring with 4 to 6 C-atoms, 
           R 3  and R 4  of formula (V) are the same or different and can be H or a linear or branched C 1 -C 12 -alkyl or R 3  and R 4  can form together a ring with 5 to 10 C-atoms, which can be part of an aliphatic or aromatic polycyclic ring system with 9 to 20 C atoms, 
           R 5  and R 6  in formula (V) are the same or different and can be H or a linear or branched C 1 -C 12 -alkyl or can form together an aliphatic ring with 5 to 8 C-atoms, 
           and R 51 , R 61  and R 7  in formula (VI) are the same or different and can be H or a linear or branched C 1 -C 12 -alkyl or two or three of R 51 , R 61  and R 7  can form together with C 1  to C 3  an aromatic ring or ring system with 6 to 14 C-atoms, 
           or mixtures therefrom. 
         
       
     
     
         5 . Process according to  claim 3 , wherein the alkoxy compound (Ax) is a reaction product of at least one compound of Group 2 metal and a monohydric alcohol (A) or a reaction product of at least one compound of Group 2 metal and a mixture of monohydric alcohol (A) with a further alcohol (B) comprising in addition to the hydroxyl moiety at least one further oxygen bearing group being different to a hydroxyl moiety. 
     
     
         6 . Process according to  claim 3 , wherein in addition to the at least one alkoxy compound (Ax) at least one alkoxy compound (Bx) being the reaction product of at least one compound of Group 2 metal and an alcohol (B) comprising in addition to the hydroxyl moiety at least one further oxygen bearing group being different to a hydroxyl moiety. 
     
     
         7 . Process according to  claim 3 , wherein the monohydric alcohols (A) are those of formula ROH in which R is a linear or branched C 1 -C 20  alkyl. 
     
     
         8 . Process according to  claim 5 , wherein in the alcohol (B) the one further oxygen bearing group is an ether moiety. 
     
     
         9 . Process according to  claim 5 , wherein the alcohol (B) is a C 2  to C 4  glycol monoether, wherein the ether moiety comprises from 2 to 18 carbon atoms. 
     
     
         10 . Process according to  claim 3 , wherein said Group 2 metal is magnesium. 
     
     
         11 . Process according to  claim 3 , wherein said transition metal is a Group 4 metal and/or Group 5 metal. 
     
     
         12 . Process according to  claim 3 , wherein the preparation of the olefin polymerisation catalyst component in form of solid particles comprises the steps of
 (a1) preparing a solution (S1) of at least one alkoxy compound (Ax), being a reaction product of at least one compound of a Group 2 metal with at least a monohydric alcohol (A) and an electron donor as defined in  claim 3  or  4 , or a corresponding precursor thereof in an organic liquid reaction medium (OM1),   (b1) combining said solution (S1) with at least one transition metal compound (CT), and   (c1) precipitating said catalyst component in the form of a solid particle, and   (d1) recovering the solidified particles of the olefin polymerisation catalyst component.   
     
     
         13 . Process according to  claim 12 , wherein the addition of solution (S1) to the at least one transition metal compound (CT) in step (b1) is done at a temperature range of 50 to 110° C., at which temperature the at least one transition metal compound (CT) is in a liquid form, resulting in the precipitation of said solid catalyst components, whereby a surfactant can be added in step (a1) or step (b1). 
     
     
         14 . Process according to  claim 12 , wherein the solution (S1) is mixed with at least one transition metal compound (CT) in liquid form at a temperature of about −20° C. to about 30° C. and precipitating the solid catalyst components by subsequently slowly raising the temperature to a temperature range of 50 to 110° C., whereby the rate of temperature increase is in the range from 0.1° C. to 30° C. per minute and whereby a surfactant is added to the solution (S1) before step (b1). 
     
     
         15 . Process according to  claim 3 , wherein the preparation of the catalyst component in form of solid particles comprises the steps of
 (a2) preparing a solution of at least one alkoxy compound (Ax), being a reaction product of at least one compound of a Group 2 metal with at least a monohydric alcohol (A) and an electron donor of formula (I) or a precursor thereof in an organic liquid reaction medium,   (b2) adding said solution of said alkoxy compound (Ax) to at least one compound of a transition metal to produce an emulsion, wherein the dispersed phase of which is in the form of droplets and contains more than 50 mol % of the Group 2 metal in said alkoxy compound (Ax),   (c2) agitating the emulsion in order to maintain the droplets of said dispersed phase within said predetermined average size range of 2 to 500 μm,   (d2) solidifying said droplets of the dispersed phase,   (e2) recovering the solidified particles of the olefin polymerisation catalyst component.   
     
     
         16 . Process for preparing propylene random copolymers according to  claim 3 , wherein said co-catalyst is an alkyl aluminum co-catalyst. 
     
     
         17 . Process according to  claim 4 , wherein said aromatic ring or ring system has 10 to 14 C-atoms. 
     
     
         18 . Process according to  claim 11 , wherein said transition metal is Ti. 
     
     
         19 . Process according to  claim 13 , wherein the rate of temperature increase is in the range from 0.5 to 10° C. per minute.