Ethylene/Alpha-Olefin Copolymers for Better Optical and Mechanical Properties and Processability of Film Made Therefrom

Abstract

A Ziegler-Natta catalyzed ethylene/alpha-olefins copolymer is provided having sporadic long chain branches and reversed comonomer composition distribution or short chain branching distribution (SCBD) in the high molecular weight fractions. According to the invention, polyethylene film made with the inventive copolymer has a balance of improved physical, optical, mechanical properties as well as processability. In one aspect, the film includes a 1% secant modulus of greater than 25,000 psi, a film haze of less than 10, a film clarity of greater than 90, a dart impart resistance of greater than 500 g/mil, and a MD tear strength of greater than 500 g/mil.

What is claimed is: 
     
         1 . A Ziegler-Natta catalyzed ethylene/alpha-olefins copolymer, wherein the copolymer comprises the following properties:
 density of between 0.890 and 0.935 g/cc;   C4-C10 comonomer content of between 1 and 20 wt %;   melt index (I2) of between 0.5 and 10 dg/min;   ratio (M z /M w ) of z-average molecular weight (Mz) to weight average molecular weight (Mw) of between 3.0 and 10;   melting point over 124° C. across the density of 0.890 to 0.935 g/cc;   sporadic long chain branches with J-C α value of less than 5;   melt strength index, defined as the ratio of storage modulus to loss modulus (G′/G″) at a shear rate of 0.03 s −1 , is less than 5;   weight average molecular weight Mw of less than 200,000 g/mol;   a fraction soluble below about 30° C. of greater than 12 wt %, determined by CRYSTAF, having a weight average molecular weight Mw of higher than 90,000 g/mol, determined by gel permeation chromatography (GPC);   a fraction soluble between about 60° C. and 75° C. of less than 35 wt %, determined by CRYSTAF;   greater than 13.5 wt % of a polymer component having an elution temperature below about 30° C., determined by temperature rising elution fractionation (TREF) analysis;   greater than 15 wt % of a polymer component having an elution temperature below about 40° C., determined by TREF analysis, and an average high molecular weight of greater than 90,000 g/mol, determined by GPC analysis;   greater than 10 wt % of a polymer component having an elution temperature range from about 30° C. to 60° C., determined by TREF analysis;   less than 50 wt % of a polymer component having an elution temperature range from about 60° C. to 94° C., determined by TREF analysis;   greater than 25 wt % of a polymer component having an elution temperature higher than about 94° C., determined by TREF analysis;   a substantially constant distribution of short chain branching across its molecular weight distribution (MWD) in each fraction over the elution temperature range from about 30° C. to 94° C., determined by GPC coupled with Fourier Transform Infrared Spectroscopy Detector (GPC-FTIR); and   a reversed distribution of comonomer composition across the molecular weight distribution in the fractions eluted over about 94° C., determined by GPC-FTIR analysis; and   a high molecular weight tail in the fractions over the elution temperature range over about 100° C.   
     
     
         2 . The copolymer of  claim 1 , wherein the alpha-olefin is 1-hexene. 
     
     
         3 . The copolymer of  claim 1 , wherein the molecular weight of the copolymer satisfies the formula: (Mw of 100° C.)/(Mw of 35° C.)=1.0 to 1.3. 
     
     
         4 . The copolymer of  claim 1 , wherein the copolymer has a sporadic long chain branches with J-C α value of less than 1. 
     
     
         5 . The copolymer of  claim 1 , wherein the copolymer has a melt strength index, defined as the ratio of storage modulus to loss modulus (G′/G″) at a shear rate of 0.03 s-1, is less than 3. 
     
     
         6 . The copolymer of  claim 1 , wherein the copolymer has a ratio (Mz/Mw) of z-average molecular weight (Mz) to average weight molecular weight (Mw) of between 3.2 and 4.5. 
     
     
         7 . The copolymer of  claim 1 , wherein the molecular weight (Mw) of the fractions eluted over about 100° C. is higher than 200,000 g/mol. 
     
     
         8 . The copolymer of  claim 1 , wherein the fractions eluted over about 100° C. is at least 5 wt % of a crystallizing polymer component. 
     
     
         9 . The copolymer of  claim 1 , wherein the copolymer is prepared by copolymerizing ethylene with one or more higher alpha-olefin comonomers in the presence of a Ziegler-Natta catalyst system comprising:
 a catalyst precursor comprising Ti, Mg, Si, halogen, and nitrogen; and   a cocatalyst selected from containing halogenated aluminum alkyl or organohalogenous aluminum compounds.   
     
     
         10 . The copolymer of  claim 9 , wherein the catalyst precursor is prepared by contacting a magnesium-based composite support with an organic silicon complex, a transition metal compound, a transition metal halide compound, a substituted aromatic compound containing nitrogen, and an alkyl halide or aromatic halide. 
     
     
         11 . The copolymer of  claim 10 , wherein the magnesium-based composite support is prepared by contacting metallic magnesium with an alkyl halide or aromatic halide in the presence of an organic silicon compound having the formula R1mSi(OR2)n, wherein R1 and R2 are C1-C20 hydrocarbyl, m=0-3, n=1-4, and m+n=4, and wherein each R1 and each R2 may be the same or different. 
     
     
         12 . The copolymer of  claim 11 , wherein the organic silicon complex is prepared by reacting an alkoxysilane ester with a halogen-substituted silane. 
     
     
         13 . The copolymer of  claim 12 , wherein the alkoxysilane ester has the formula R2mSi(OR3)n, wherein R2 and R3 are independently selected from any C1-C20 hydrocarbyl, m is 0-3, n is 1-4, and m+n=4. 
     
     
         14 . The copolymer of  claim 12 , wherein the halogen-substituted silane has the formula R3xSiXy, wherein R3 is C1-C20 hydrocarbyl, X is halogen, x=0-3, y=1-4, and x+y=4, and wherein each X and each R3 may be the same or different. 
     
     
         15 . The copolymer of  claim 10 , wherein the transition metal compound has the formula M(OR4)aX4-a, wherein M is an early transition metal, wherein R4 is C1-C20 hydrocarbyl, X is a halogen, and 0≤a≤4. 
     
     
         16 . The copolymer of  claim 15 , wherein the early transition metal is titanium. 
     
     
         17 . The copolymer of  claim 10 , wherein the transition metal halide compound having the formula MX4, wherein M is an early transition metal, and X is a halogen. 
     
     
         18 . The copolymer of  claim 17 , wherein the early transition metal is titanium. 
     
     
         19 . The copolymer of  claim 10 , wherein the substituted aromatic compound containing nitrogen is selected from 2,6-dimethylpyridine, 8-quinolinol, and 2-methyl-8-quinolinol. 
     
     
         20 . The copolymer of  claim 10 , wherein the alkyl halide or aromatic halide has the formula R5X, wherein R5 is C1-C20 hydrocarbyl. 
     
     
         21 . The copolymer of  claim 9 , wherein the cocatalyst is a combination of alkyl aluminum or alkylaluminoxane and halogenated aluminum alkyl. 
     
     
         22 . The copolymer of  claim 21 , wherein the alkyl aluminum is triethyl aluminum. 
     
     
         23 . The copolymer of  claim 21 , wherein the alkylaluminoxane is selected from methylalumoxane, modified methylalumoxane, tetraethyldialumoxane, tetrabutylalumoxane, bis(diisobutylaluminum) oxide, ethylalumoxane, isobutylalumoxane, polymethylalumoxane, and mixtures or combinations thereof. 
     
     
         24 . The copolymer of  claim 21 , wherein the halogenated aluminum alkyl is selected from dimethylaluminum chloride, diethylaluminum halides, such as dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, di(t-butyl)aluminum chloride, diamylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, isobutylaluminum dichloride, ethylaluminium sesquichloride, t-butylaluminum dichloride and amylaluminum dichloride, and mixtures or combinations thereof. 
     
     
         25 . The copolymer of  claim 1 , wherein the copolymer is prepared by copolymerizing ethylene with one or more higher alpha-olefin comonomers in the presence of a prepolymer and hydrogen without using additional co-catalyst. 
     
     
         26 . The copolymer of  claim 25 , wherein the prepolymer is prepared with (co)polymerization of ethylene or alpha olefins in the presence of Ziegler-Natta catalyst system, comprising:
 a Ziegler-Natta catalyst, which is prepared by prepared by contacting a magnesium-based composite support with an organic silicon complex, a transition metal compound, a transition metal halide compound, a substituted aromatic compound containing nitrogen, and an alkyl halide or aromatic halide; and   a cocatalyst, a halogenated aluminium alkyl and/or an organohalogenous aluminum compound obtained in-situ by reacting alkyl aluminium or alkylaluminoxane with halogenated alkylaluminum compounds.   
     
     
         27 . The copolymer of  claim 26 , wherein the prepolymer has a polymer amount ranging from 0.1 to 1000 g per g of the said solid catalyst precursor. 
     
     
         28 . The copolymer of  claim 26 , wherein the prepolymer is characterized by its sporadic long chain branches in the high molecular weight fractions with a J-C α value of less than about 5. 
     
     
         29 . The copolymer of  claim 26 , wherein the prepolymer has an average particle size range from about 10 to about 500 micron, and a bulk density of between about 0.28 and 0.45. 
     
     
         30 . The copolymer of  claim 26 , wherein the prepolymer has an Al/Ti ratio of from about 1.5 to 10. 
     
     
         31 . The copolymer of  claim 1 , wherein the copolymer can be used to produce a blown film having a thickness of 1 mil (25 μm); a haze, determined by ASTM D-1003, ranging from about 6 to 15; a gloss, determined by ASTM D-2457, ranging from about 80-100; dart impart, determined by ASTM D-1709, ranging from about 450 to 800; and MD tear strength, determined by ASTM D-1922, ranging from about 400 to 600.