Process for preparing copolymers and blend compositions containing the same

Abstract

Disclosed is a novel ethylene copolymer by copolymerizing an ethylene and at least one comonomer selected from a compound represented by the formula H 2 C═CHR wherein R is, for example, an alkyl group or an aryl group, and a diene, by slurry polymerization process in the presence of a solid catalyst system comprising a support, a transition metal compound and an activator capable of converting the transition metal compound into a catalytically active transition metal complex.

1 . An ethylene copolymer comprising a copolymer of ethylene with at least one comonomer selected from the group consisting of a compound represented by the formula H 2 C═CHR wherein R is a C 1 -C 20  linear, branched or cyclic alkyl group or a C 6 -C 20  aryl group, and a C 4 -C 20  linear, branched or cyclic diene, prepared by a process, which process comprises copolymerizing said ethylene with said comonomer by slurry polymerization in the presence of a solid catalyst system comprising: a support, a transition metal compound, and an activator capable of converting the transition metal compound into a catalytically active transition metal complex;
 wherein said ethylene copolymer has the following properties (1) to (4):
 (1) a density d (g/cm 3 ) of from 0.870 to 0.980; 
 (2) an M w /M n  of from 2.5 to 10, wherein M w  and M n  are, respectively, a weight average molecular weight and a number average molecular weight, both as measured by gel permeation chromatography (GPC); 
 (3) when, in cross fractionation chromatography (CFC) of said ethylene copolymer, with respect to extraction at an arbitrary temperature T(° C.) falling within the range of between a first temperature at which a maximum amount of extraction is exhibited and a second temperature which is the lower temperature of either the temperature of 10° C. higher than said first temperature or 96° C., the relationship between said arbitrary temperature T(° C.) and a point in molecular weight on a molecular weight distribution profile of a copolymer fraction extracted at said arbitrary temperature T(° C.) at which point in molecular weight said molecular weight distribution profile of the copolymer fraction shows a peak having a maximum intensity is treated by the least squares method to obtain an approximate straight line within the range of between said first temperature and said second temperature; if there is the copolymer fraction the amount of which is less than 1% by weight on the total amount, excluding purge, of copolymer fractions extracted at temperatures in the overall range of extraction temperatures in CFC, the copolymer fraction can be excluded from the calculation for the approximate straight line; the approximate straight line has a gradient within the range defined by the formula (I):
   −1≦{log  Mp ( T   1 )−log  Mp ( T   2 )}/( T   1   −T   2 )≦−0.005  (I) 
 wherein: 
 T 1  and T 2  are two different arbitrary extraction temperatures T(° C.) within the range of between said first temperature and said second temperature, and 
 Mp(T 1 ) and Mp(T 2 ) are, respectively, molecular weights corresponding to T 1  and T 2  on said approximate straight line; and 
 
 (4) the measurement of said ethylene copolymer by CFC shows characteristics such that the sum of respective amounts of copolymer fractions extracted at temperatures which are at least 10° C. lower than said first temperature as defined above is 8% by weight or less, based on the total amount, excluding purge, of copolymer fractions extracted at temperatures in the overall range of extraction temperatures in CFC. 
   
     
     
         2 . The ethylene copolymer according to  claim 1 ; wherein the Mw/Mn ratio satisfies the following inequality;
   1.25 log  Mw −2.5 ≦Mw/Mn≦ 3.50 log  Mw −11.0.   
     
     
         3 . The ethylene copolymer according to  claim 1 , wherein, said ethylene copolymer has the following property (5) with the properties (1), (2), (3) and (4);
 (5) within a range in molecular weight of said ethylene copolymer which is defined by the formula (II):
   log( Mt )−log( Mc )≦0.5  (II) 
 wherein: 
 Mt is a point in molecular weight on a molecular weight distribution profile at which said profile shows a peak having a maximum intensity, and 
 Mc is an arbitrary point in molecular weight on said molecular weight distribution profile, 
 and wherein said molecular weight distribution profile is obtained together with a comonomer content distribution profile by subjecting said ethylene copolymer to gel permeation chromatography/Fourier transformation infrared spectroscopy (GPC/FT-IR), then 
 an approximate straight line obtained from said comonomer content distribution profile by the least squares method has a gradient within the range defined by the formula (III):
   0.0005≦{ C ( Mc   1 )− C ( Mc   2 )}/(log  Mc   1 −log  Mc   2 )≦0.05  (III) 
 
 wherein: 
 Mc 1  and Mc 2  are two different arbitrary points (Mc) in molecular weight which satisfy the formula (II), and 
 C(Mc 1 ) and C(Mc 2 ) are, respectively, comonomer contents corresponding to Mc 1  and Mc 2  on said approximate straight line 
   
     
     
         4 . The ethylene copolymer according to any of  claims 1  to  3 , wherein the M w /M n  ratio is of from 3 to 7. 
     
     
         5 . The ethylene copolymer according to any of  claims 1  to  4 , wherein, with respect to property (3), said approximate straight line obtained from said molecular weight distribution profile obtained by CFC of said polymer fraction has a gradient with the range defined by the following formula (IV):
   −0.1≦{log  Mp ( T   1 )−log  Mp ( T   2 )}/( T   1   −T   2 )≦−0.01  (IV)   wherein T 1 , T 2 , Mp(T 1 ) and Mp(T 2 ) are as defined for formula (I) above.   
     
     
         6 . The ethylene copolymer according to any of  claims 3  to  5 , wherein, with respect to property (5), said approximate straight line obtained from said comonomer content distribution profile obtained by GPC/FT-IR of said ethylene comonomer has a gradient within the range defined by the following formula (V):
   0.001≦{ C ( Mc   1 )− C ( Mc   2 )}/(log Mc 1 −log  Mc   2 )≦0.02  (V)   wherein Mc 1 , Mc 2 , C(Mc 1 ) and C(Mc 2 ) are as defined for formula (III) above.   
     
     
         7 . The ethylene copolymer according to any of  claims 1  to  6 , wherein, with respect to property (4), said sum of respective amounts of copolymer fractions extracted at temperatures which are at least 10° C. lower than said first temperature is 5% by weight or less, based on the total amount, excluding purge, of copolymer fractions extracted at temperatures in the overall range of extraction temperatures in CFC. 
     
     
         8 . A process for preparing the ethylene copolymer of any of  claims 1  to  7 , which process comprises copolymerizing said ethylene with said comonomer by slurry polymerization in the presence of a solid catalyst system comprising: a support, a transition metal compound, and an activator capable of converting the transition metal compound into a catalytically active transition metal complex. 
     
     
         9 . The process according to  claim 8  wherein said solid catalyst system comprises:
 a supported catalyst component comprising;
 (a) a support material, an organometal compound wherein the metal is selected form Groups 2-13 of the Periodic Table of the Elements, germanium, tin, and lead; and 
 (b) an activator compound comprising (b-1) a cation which is capable of reacting with a transition metal compound to form a catalytically active transition metal complex, and 
 (c) a compatible anion (b-2) having up to 100 nonhydrogen atoms and containing at least one substituent comprising an active hydrogen moiety; and 
   (d) a transition metal compound.   
     
     
         10 . The process according to  claim 8 , wherein the cation (b-1) is selected from the group consisting of Brønsted acidic cations, carbonium cations, silylium cations, and cationic oxidizing agents, and in the anion (b-2) the substituent comprising an active hydrogen moiety corresponds to the following formula (VI):
   G q (T-H) r   (VI)   wherein;   G is a polyvalent hydrocarbon radical,   T is O, S, NR, or PR, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbyl germyl radical or hydrogen,   q is 0 or 1, and   r is an integer from 1 to 3.   
     
     
         11 . The process according to  claim 9  wherein the compatible anion portion of the activator compound corresponds to the following formula (VII):
   [M′ m+ Q n (G q (T-H) r ) z ] d−   (VII)   wherein;   M′ is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements;   Q independently in each occurrence is selected from the group consisting of hydride, dihydrocarbylamido, halide, hydrocarbyloxide, hydrocarbyl, and substituted-hydrocarbyl radicals, including halo-substituted hydrocarbyl radicals, and hydrocarbyl- and halohydrocarbyl-substituted organo-metalloid radicals, the hydrocarbyl portion having from 1 to 20 carbons with the proviso that in not more than one occurrence is Q halide;   G is a polyvalent hydrocarbon radical having r+1 valencies bonded to M′ and T; wherein   T is O, S, NR, or PR, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbyl germyl radical or hydrogen;   m is an integer from 1 to 7;   n is an integer from 0 to 7;   q is an integer of 0 or 1;   r is an integer from 1 to 3;   z is an integer from 1 to 8;   d is an integer from 1 to 7; and
     n+z−m=d.    
   
     
     
         12 . The process according to any of  claims 8  to  10  wherein the solid catalyst system is obtained by combining:
 (1) a supported catalyst component obtained by
 (A) subjecting the support material to a thermal treatment at 100° C. to 1000° C.; combining the thermally treated support material with the organometal compound in a suitable diluent or solvent; and subsequently combining the resulting product with the activator compound; or 
 (B) combining the activator compound with the organometal compound to form an adduct; and combining the adduct with the support material; or 
 (C) combining a water containing support material with the organometal compound; and combining the resulting product with 
 (D) the activator compound; and 
 (E) a transition metal compound. 
   
     
     
         13 . The process according to  claim 8 , wherein the solid catalyst system comprises a supported catalyst component which results from admixing;
 (a) a support material and an alumoxane which component contains 15 to 40 weight percent of aluminum, based on the total weight of the support material and alumoxane, which is obtained by;
 (i) heating said support material and alumoxane under an inert atmosphere for a period and at a temperature sufficient to fix alumoxane to the support material, to provide a supported catalyst component wherein not more than 10 percent aluminum present in the supported catalyst component is extractable in a one-hour extraction with toluene at 90° C. using 10 ml toluene per gram of supported catalyst component; and 
 (ii) optionally, subjecting the product produced in step (a) to one or more wash steps to remove alumoxane not fixed to the support material; and 
   (b) a transition metal compound.   
     
     
         14 . The process according to any of  claims 8  to  13 , wherein the transition metal compound contains at least one cyclic or noncyclic π-bonded anionic ligand group. 
     
     
         15 . The process according to  claim 14 , wherein said transition metal compound is a bridged monocyclopentadienyl or mono (substituted cyclopentadienyl) transition metal compounds represented by: the following formula (VII): 
       
         
           
           
               
               
           
         
         wherein: 
         M is a metal of groups 3-5, especially a group 4 metal, particularly titanium; 
         Cp* is a substituted cyclopentadienyl group bound to Z′ and, in an η 5  bonding mode, to M or such a group is further substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amine, and mixture thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two such further substituents together cause Cp* to have a fused ring structure; 
         Z′ is a divalent moiety other than a cyclic or noncyclic π-bonded anionic ligand, said Z′ comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally nitrogen, phosphorus, sulfur or oxygen, said moiety having up to 20 non-hydrogen atoms, and optionally Cp* and Z′ together form a fused ring system; 
         X independently in each occurrence represents an anionic ligand group (other than a cyclic, aromatic π-bonded anionic ligand group) selected from the group of hydrocarbyl, hydrocarbylene (including hydrocarbadienyl), hydrocarbyloxy, hydride, halo, silyl, germyl, amide, and siloxy radicals having up to 50 nonhydrogen atoms; and 
         n is 1 or 2 depending on the valence of M; or by the following formula (X): 
       
       
         
           
           
               
               
           
         
         wherein: 
         M is titanium or zirconium in the +2 formal oxidation state; 
         L is a group containing a cyclic, delocalized, anionic, π-system through which the group is bonded to M, and which group is also bonded to Z; 
         Z is a moiety bonded to M via a σ-bond, comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen, said moiety having up to 60 non-hydrogen atoms; and 
         X* is a neutral, conjugated or nonconjugated diene, optionally substituted with one or more hydrocarbyl groups, said X having up to 40 carbon atoms and forming a π-complex with M. 
       
     
     
         16 . The process according to any of  claims 8  to  15 , wherein the support material is selected from the group consisting of silica, alumina, mixed oxides of silica and one or more Group 2 or 13 metal oxides, alumina, magnesia, and titania. 
     
     
         17 . A polymer blend composition comprising;
 (I) from 1 to 99% by weight based on the combined weight of Components (I) and (II) of the ethylene copolymer of any of  claims 1  to  7 ; and   (II) from 1 to 99% by weight based on the combined weight of Components (I) and (II) of either
 (1) an ethylene homopolymer which has been prepared with a catalyst component other than that used in the process of any of  claim 8  to  16 , or 
 (2) an ethylene/α-olefin copolymer which is different from that of component (I). 
   
     
     
         18 . The polymer blend composition of  claim 17 , wherein
 (I) Component (I) is said ethylene copolymer of any of  claims 1  to  7  prepared by the process of any of  claims 8  to  16 ; and   (II) Component (II) comprises;
 (1) an ethylene homopolymer prepared by a catalyst component other than said catalyst component of any of  claim 8  to  16 ; or 
 (2) a homogeneous narrow composition distribution ethylene/α-olefin interpolymer; or 
 (3) a heterogeneous broad composition distribution ethylene/α-olefin interpolymer; or 
 (4) the ethylene/α-olefin copolymer (I) having a different I 2 , or density, or M w , or M w /M n ; or 
 (5) a combination of any two or more of (II)(1), (II)(2), or (II)(3) or (II)(4). 
   
     
     
         19 . The polymer blend composition of  claim 18  having;
 1) a density of from 0.870 to 0.980 g/cm 3 ,   2) a melt index, (I 2 ), of from 0.0001 to 10000 g/10 min,   3) an I 10 /I 2  ratio of from 5 to 100, or an I 21.6 /I 2  ratio of from 20 to 200, and   4) an M w /M n  of from 5 to 50; and wherein
 (a) Component (I) is said ethylene copolymer of any of  claims 1  to  7 ; and is present in an amount of from 10 to 90% by weight based on the combined weight of Component (I) and Component (II); and
 i) has a density of from 0.870 to 0.980 g/cm 3 , 
 ii) a melt index (I 2 ) of from 0.0001 to 10000 g/10 min, 
 iii) an I 10 /I 2  ratio of from 5 to 30, or an I 21.6 /I 2  ratio of from 15 to 65, 
 iv) an M w /Mn of from 2.5 to 10; and 
 
 (b) Component (II) is present in an amount of from 10 to 90% by weight based on the combined weight of Component (I) and Component (II); and has;
 i) a density of from 0.915 to 0.985 g/cm 3 , 
 ii) a melt index (I 2 ) of from 0.0001 to 10000 g/10 min; and 
 
 (c) Component (II)(1) when present has
 i) an I 10 /I 2  of from 5 to 40, or an I 21.6 /I 2  of from 15 to 80, and 
 ii) an M w /M n  of from 2.5 to 12; and 
 
 (d) Component (II) (2) when present when present has an I 10 /I 2  of from 5 to 25, or an I 21.6 /I 2  of from 10 to 50; and 
 (e) Component (II)(3) when present has;
 i) an I 10 /I 2  of from 5 to 40 or an I 21.6 /I 2  of from 15 to 80, and 
 ii) an M w /M n  of from 3 to 12; and 
 
 (f) Component (II)(4) when present has;
 i) an I 10 /I 2  of from 5 to 30, or an I 21.6 /I 2  of from 15 to 55, and 
 ii) an M w /M n  of from 2.5 to 10. 
 
   
     
     
         20 . The polymer blend composition of  claim 18  having
 1) a density of from 0.915 to 0.975 g/cm 3 ,   2) a melt index, (I 2 ), of from 0.001 to 5000 g/10 min,   3) an I 10 /I 2  ratio of from 5 to 90, or an I 21.6 /I 2  ratio of from 30 to 180, and   4) an M w /M n  of from 3 to 45; and wherein
 (a) Component (I) is said ethylene copolymer of any of  claims 1  to  7 ; and is present in an amount from 25 to 75% by weight based on the combined weight of Components (I) and Component (II); and has;
 i) a density of from 0.890 to 0.965 g/cm 3 , 
 ii) a melt index, (I 2 ), of from 0.001 to 5000 g/10 min, 
 iii) an I 10 /I 2  ratio of from 5 to 28, or an I 21.6 /I 2  ratio of from 18 to 55, 
 iv) an M w /Mn of from 2.8 to 8; and 
 
 (b) Component (II) is present in an amount from 25 to 75% by weight based on the combined weight of Components (I) and Component (II); and has a density of from 0.935 to 0.983 g/cm 3 , and a melt index (I 2 ) of from 0.001 to 5000 g/10 min; and 
 (c) Component (II)(1) when present has an
 i) an I 21.6 /I 2  of from 18 to 70 or an I 10 /I 2  of from 5.3 to 35, 
 ii) an M w /M n  of from 2.8 to 10; and 
 
 (d) Component (II) (2) when present has an I 10 /I 2  ratio of from 5.3 to 25, or an I 21.6 /I 2  of from 12 to 45; and 
 (e) Component (II)(3) when present has;
 i) an I 10 /I 2  ratio of from 5.3 to 35, or an I 21.6 /I 2  of from 20 to 70, and 
 ii) an M w /M n  of from 3.5 to 10; and 
 
 (f) Component (II)(4) when present has;
 i) an I 10 /I 2  ratio of from 5.3 to 28, or an I 21.6 /I 2  of from 18 to 45, and 
 ii) an M w /M n  of from 2.8 to 8. 
 
   
     
     
         21 . The polymer blend composition of  claim 18  having;
 1) a density of from 0.935 to 0.970 g/cm 3 ,   2) a melt index, (I 2 ), of from 0.01 to 3000 g/10 min,   3) an I 10 /I 2  ratio of from 5 to 80, or an I 21.6 /I 2  ratio of from 40 to 150, and   4) an M w /M n  of from 5 to 40; and wherein
 (a) Component (I) is said ethylene copolymer of any of  claims 1  to  3 ; and is present in an amount from 35 to 65% by weight based on the combined weight of Component (I) and Component (II); and has;
 i) a density of from 0.915 to 0.955 g/cm 3 , 
 ii) a melt index (I 2 ) of from 0.01 to 3000 g/10 min, 
 iii) an I 10 /I 2  ratio of from 5.5 to 25, or an I 21.6 /I 2  ratio of from 20 to 50, and 
 iv) an M w /Mn of from 3 to 7; and 
 
 (b) Component (II) is present in an amount from 35 to 65% by weight based on the combined weight of Component (I) and Component (II), and has a density of from 0.955 to 0.980 g/cm 3 , and a melt index (I 2 ) of from 0.01 to 3000 g/10 min; and 
 (c) Component (II)(1) when present has;
 i) an I 21.6 /I 2  of from 20 to 60, or an I 10 /I 2  of from 5.5 to 30; and 
 ii) an M w /M n  of from 3 to 9; and 
 
 (d) Component (II)(2) when present has;
 i) an I 10 /I 2  ratio of from 5.5 to 20, or an I 21.6 /I 2  of from 15 to 40, and 
 ii) has an M w /M n  less than 3; and 
 
 (e) Component (II)(3) when present has;
 i) an I 10 /I 2  ratio of from 5.5 to 30, or an I 21.6 /I 2  of from 25 to 60, and 
 ii) an M w /M n  of from 4 to 9; and 
 
 (f) Component (II)(4) when present has;
 i) an I 10 /I 2  ratio of from 5 to 30, or an I 21.6 /I 2  of from 20 to 50, and 
 ii) an M w /M n  of from 3 to 7. 
 
   
     
     
         22 . The polymer blend composition of  claim 18 , wherein Component (II)(2) contains long chain branches. 
     
     
         23 . The polymer blend composition of  claim 18 , wherein Component (II)(2) contains long chain branches in the range of 0.01 to 3 per 1000 carbon atoms. 
     
     
         24 . The polymer blend composition of  claim 18 , wherein Component (I) has a lower density and a higher molecular weight than Component (II). 
     
     
         25 . The polymer blend composition of  claim 18 , wherein Component (II)(2) contains long chain branches in the range of 0.1 to 3 per 1000 carbon atoms. 
     
     
         26 . A process for forming a polymer blend composition, which process comprises the steps of:
 (A) preparing an ethylene/α-olefin copolymer (I) by the process of any of  claims 8  to  16 ;   (B) contacting under polymerization conditions a feedstream comprising ethylene, optionally at least one α-olefin comonomer, and an ethylene polymerization catalyst, to form (II) an ethylene homopolymer which has been prepared with a catalyst component other than that used in the process of any of  claims 8  to  16 , or an ethylene/α-olefin copolymer; and   (C) combining the ethylene/α-olefin copolymer (I) with the ethylene homopolymer or ethylene/α-olefin interpolymer (II) to form (III) the polymer blend composition.   
     
     
         27 . The process of  claim 26  wherein steps (A) and (B) are performed in different reactors. 
     
     
         28 . The process of  claim 26  wherein the reactors are operated in series and step (A) is performed in the first reactor(s) and step (B) is performed in the second reactor(s) 
     
     
         29 . The process of  claim 26  wherein the reactors are operated in series and step (B) is performed in the first reactor(s) and step (A) is performed in the second reactor(s). 
     
     
         30 . The process of  claim 26  wherein;
 (a) step (B) is performed under slurry phase polymerization conditions, or solution phase polymerization conditions, or gas phase polymerization conditions; and   (b) the ethylene polymerization catalyst used in step (B) is a catalyst described in  claims 8  to  16 , or a Ziegler catalyst, or an unsupported single site catalyst, or a supported single site catalyst other than that described in  claims 8  to  16 , or a mixture of any two or more of said ethylene polymerization catalysts.   
     
     
         31 . The process of  claim 26  wherein the ethylene polymerization catalyst of step (B) is a Ziegler ethylene polymerization catalyst comprising;
 (a) a solid support component is a magnesium halide or silica, and   (b) a transition metal component represented by the formulas;
   TrX′ 4-q (OR 1 ) q , TrX′ 4-q R 2   q , VOX′3 and VO(OR 1 ) 3 , 
 wherein: 
 Tr is a Group IVB, VB, or VIB metal, 
 q is 0 or a number equal to or less than 4, 
 X′ is a halogen, and 
 R 1  is an alkyl group, aryl group or cycloalkyl group having from 1 to 20 carbon atoms, and 
 R 2  is an alkyl group, aryl group, aralkyl group, or substituted aralkyl group. 
   
     
     
         32 . The process of  claim 26  wherein the reactors are operated in parallel. 
     
     
         33 . The process of  claim 26 , wherein Component I has a lower density and a higher molecular weight than Component II. 
     
     
         34 . The process of  claim 26  wherein the comonomer of step (B) is a C 3 -C 20  α-olefin. 
     
     
         35 . The process of  claim 26  wherein the comonomer of steps (A) and (B) is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-octene, or 1-hexene. 
     
     
         36 . The process of  claim 26  wherein the comonomer of steps (A) and (B) is 1-hexene or 1-octene. 
     
     
         37 . The polymer blend composition prepared by the process of  claim 26 . 
     
     
         38 . The sintering powder made from the ethylene copolymer of any of  claims 1  to  7 . 
     
     
         39 . A fabricated article made from the polymer blend composition of any of  claims 17  to  25 . 
     
     
         40 . A fabricated article of  claim 39  which is in the form of a film, fiber, or sheet, or the result of a thermoforming, blow molding, injection molding and rotational molding process. 
     
     
         41 . A fabricated article of  claim 39  comprising pipes, tubing, cable or wire jackets, pipe coatings, geomembranes, thermoformed articles, stackable plastic pallets, blow molded bottles or containers, or environmental pond liners.