Abstract:
Organic compounds containing heteroatoms and their use in preparing Ziegler-Natta(Ziegler-Natta) catalyst with single activation center. The Ziegler-Natta olefin polymerization catalyst is preparing by adding organic or inorganic solid carrier or compound of them which is pre-activated by heating or pre-treated chemically, organic compound containing heteroatoms and metallic compound into magnesium compound/tetrahydrofuran solution. The Ziegler-Natta olefin polymerization catalyst prepared in the present invention is fluidizable powder and can prepare ethene homopolymer and copolymer of controllable construction with high catalytic activity, during homo-polymerization and combined polymerization with alpha-olefin of C 3 ˜C 18  under action of catalyst promoter such as alkyl aluminum, alkyl aluminoxane, and so on.

Description:
CROSS-REFERENCE AND RELATED APPLICATIONS 
       [0001]    The subject application is a divisional application of U.S. patent application Ser. No. 12/275,882 filed on Nov. 21, 2008, which is in turn a continuation-in-part of PCT/CN2007/001648 filed on May 21, 2007 and published as WO 2007/134537 on Nov. 29, 2007, which in turn claims priority on Chinese Patent Application CN 200610026766.2 filed on May 22, 2006. The subject matter and contents of all the above-mentioned priority applications are incorporate herein by reference in their entirety. 
     
    
     FIELD OF THE INVENTION 
       [0002]    The present invention provides a new class of organic compounds containing heteroatom, their syntheses, and applications as donor in preparing single-site Ziegler-Natta catalysts. Upon activation with alkyl aluminum, alkyl aluminoxane (MAO), or modified alkyl aluminoxane (MMAO), the single-site Ziegler-Natta catalysts can efficiently promote ethylene polymerization or ethylene/α-olefin copolymerization to provide high-performance polyolefin materials. 
       BACKGROUND OF THE INVENTION 
       [0003]    With the rapid development of polyolefin industry, much more extensive attention have been paid to the production of high-performance polyolefin materials. High-performance polyolefin materials can be prepared mainly in two ways: 1) by excellent single-site catalyst; 2) by advanced technology process. With single-site catalyst (homogeneous catalysts), the properties of polymer could be controlled well and so a variety of high-performance polyolefin materials are provided. However, metal complexes as the real active species of single-site catalysts are unstable, difficult to be synthesized, and difficult in exhibiting their original characters after supported on carrier. All of these difficulties largely limit the applications and development of single-site catalysts. In addition to the aforementioned challenge, a large number of expensive cocatalysts such as alkyl aluminoxane (such as MMAO) is always needed to get high activity. 
         [0004]    Compared to the single-site metallocene and non-metallocene catalysts, Ziegler-Natta catalyst are still the most important catalyst now. The main reason is closely related to their stability, simple preparation and low cost. However, because of the character of having multi active sites in Ziegler-Natta catalyst, the polymer structure can not be controlled well when Ziegler-Natta catalyst is used. In recent years, by using advanced Ziegler-Natta catalysts and chemical technology processes, polyolefin materials with excellent performance can be produced. For example: U.S. Pat. No. 5,459,116 discloses a kind of olefins polymerization catalyst. The catalyst is prepared by directly reacting a magnesium compound of liquid phase having no reducing power with a titanium compound of liquid phase in the presence of at least one electron donor, which contains at least one hydroxyl group. Superior in activity as well as production yield in polymerizing olefins, the catalyst is capable of not only providing the polymer with high stereoregularity but also improving the bulk density of the polymer, especially polyethylene; U.S. Pat. Nos. 5,106,807 and 4,330,649 disclose the activity of catalysts and polymer molecular weight can be controlled by the addition of ester compounds; CN1189487C(PCT/KR2000/001549) provides a method to prepare ethylene homopolymers and copolymers with narrow molecular weight distributions 3.6-4.3; Terano reported Ziegler-Natta catalysts supported either on surface functionalized SiO 2  or on ethylene/propylene/diene elastomers (EPDM). The molecular weight distribution of polyethylenes varied from narrow to broad (1.6-30) by solely changing the type of Al-alkyl cocatalyst. This is the narrowest molecular weight distribution obtained by Ziegler-Natta catalyst (Terano, M.  Catalysis Commun.  2003, 4, 657-662 ; Macromol. Chem. Phys.  1998, 199, 1765), however, either the activity of catalyst or the polymer molecular weight decreased significantly. 
       SUMMARY OF THE INVENTION 
       [0005]    The purpose of the invention is to provide a new class of organic compounds containing heteroatoms. 
         [0006]    The purpose of the invention is also to provide the application of the organic compounds as electronic donors in the preparation of the single-site Ziegler-Natta catalyst. 
         [0007]    The purpose of the invention is also to provide a new class of single-site Ziegler-Natta catalysts and their preparation methods. 
         [0008]    The purpose of the invention is to provide the usage of the catalysts and the catalysts systems. The catalysts and the catalysts systems are highly active to catalyze the ethylene polymerization or copolymerization with α-olefin of C 3 -C 18 , with good control of the polymer molecular weight and well comonomer distribution. The molecular weight distribution (PDI) of the obtained polymer is narrow (PDI 1.6 to 5.0). 
         [0009]    The present invention provides a new class of organic compounds containing heteroatoms and their applications as electron donors in the preparation of single-site Ziegler-Natta catalyst, along with magnesium compound and metal compound or/and supporter. The organic compounds may be easily synthesized in high yields under mild conditions by refluxing the corresponding 1,3-diketone derivatives with amine derivatives in organic solvents for 2-48 hours. 
         [0010]    Upon activation with cocatalysts such as alkyl aluminum, the prepared single-site Ziegler-Natta catalysts are highly active for ethylene polymerization or copolymerization with α-olefin of C 3 -C 18 , with the highest activity of ethylene polymerization up to 18000 g polymer/g catalyst; the incorporation ratio of comonomer such as 1-hexene can be higher than 2.0 mol %. The molecular weight distribution of the resulting polymer is narrow (PDI 1.6 to 5.0), and the structure of the polymer is controllable. All of the distinguish characters make the catalyst suitable for commercialization. 
         [0011]    The structure of the organic compounds containing heteroatoms is shown below (I), and in organic solvents which may be a mixture of two tautomerisms I and II: 
         [0000]    
       
                 
         
             
             
         
       
     
       DETAILED DESCRIPTION OF THE INVENTION 
       [0012]    The organic compounds containing heteroatoms provided in the present invention are showed below: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    in the compound, R 1  and R 2 , respectively, is H, hydrocarbyl of C 1 -C 30 , substituted hydrocarbyl of C 1 -C 30 , aryl group of C 5 -C 50 , or substituted aryl group of C 5 -C 50 , while these groups may be same or different; 
         [0013]    R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 , respectively, is H, hydrocarbyl group of C 1 -C 30 , substituted hydrocarbyl group of C 1 -C 30 , aryl group of C 5 -C 50 , or substituted aryl group of C 5 -C 50 , while these groups may be same or different, of which, R 4 , R 5  with R 6  or R 7 , R 6  with R 8  or R 9 , R 7  with R 8  or R 9  may form a bond or form a cycle; 
         [0014]    X is O, N, S, Se or P; 
         [0015]    when X is O, S or Se, there is only one group R 8  or R 9  on X; 
         [0016]    the aryl group is phenyl, naphthyl or other heteroaromatic group; the substituted hydrocarbyl group or substituted aryl group is the group substituted with hydrocarbyl, halogen, carbonyl group, ester group, group containing silicon, group containing oxygen atom —OR 10 , group containing sulfur atom —SR 11  or —S(O)R 12 , group containing nitrogen atom —NR 13 R 14  or —N(O)R 15 R 16 , or group containing phosphorous atom —PR 17 R 18  or —P(O)R 19 R 20 , group containing selenium atom —SeR 21  or —Se(O)R 22 ; 
         [0017]    R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21  or R 22  is substituted hydrocarbyl group of C 1 -C 30 , aryl group of C 5 -C 50 , of them, R 13  and R 14 , R 15  and R 16 , R 17  and R 18 , R 19  and R 20  can link to one another to form covalent bond or to form a ring; 
         [0018]    The organic compound containing heteroatom in the present invention has a structure of following general formula (I), and which can be a mixture of I and II in organic solvents: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0019]    R 1 -R 9  are the groups as aforementioned. 
         [0020]    Examples representative of compound I include ED01-ED44, and it needs to emphasize that the compound provided in present invention is not limited to these examples: 
         [0000]    
       
                 
         
             
             
         
       
       
                 
         
             
             
         
       
       
                 
         
             
             
         
       
       
                 
         
             
             
         
       
       
                 
         
             
             
         
       
       
                 
         
             
             
         
       
       
                 
         
             
             
         
       
     
         [0021]    One organic compound or a mixture of two or more of compounds mentioned above can be used as electron donor (ED) in preparing single-site Ziegler-Natta catalyst. 
       Preparation of the Organic Compound Containing Heteroatom 
       [0022]    The organic compound can be synthesized according to literature methods (Hu W.-Q. et. al.,  Organometallics  2004, 23, 1684-1688; Wang, C. et. al.  Macromol. Rapid Commun.  2005, 26, 1609-1614). 
         [0023]    In the present invention, the compound is prepared in organic solvent by mixing the diketone derivative(III) with amine derivative (IV) in the presence of catalyst as showed below. The mixture is refluxed for 2-48 hrs, and after removing the solvent, the residue is purified by recrystallization in alcohol solvent to get compound (I). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0024]    The catalyst in the reaction is formic acid, acetic acid, TsOH, or the other organic acid; the organic solvent is methanol, ethanol, or others, and anhydrous ethanol is optimal; 
         [0025]    the molar ratio of diketone, amine, and catalyst is 1-1.5:1:0.01-0.1; 
         [0026]    diketone is described by formula (III): 
         [0000]    
       
                 
         
             
             
         
       
     
         [0027]    amine can be described by formula (IV): 
         [0000]    
       
                 
         
             
             
         
       
     
         [0028]    R 1 -R 9  are the groups as those mentioned above. 
         [0029]    In the present invention, the single-site Ziegler-Natta catalyst is made of magnesium compound, supporter, metal complex, and the organic compound containing heteroatom, and the content of metal is in the range of 0.1-15 wt %. 
         [0030]    The magnesium compound can be magnesium halide, alkyl magnesium, alkoxy magnesium halide, alkoxy magnesium or magnesium halide coordinate alcohol. Of the above named magnesium compound, a mixture of two or more may also be used; the magnesium halide or alkyl magnesium is the optimum. 
         [0031]    The supporter of the single-site Ziegler-Natta catalyst can be organic material, metal oxides of group 2, 4, 13, and 14, clay, or molecular sieve. The metal oxides may be Al 2 O 3 , SiO 2 , or a mixture of two or more metal oxides. 
         [0032]    The “metal complex” can be represented by the formula (V): 
         [0000]      ML a   (V)
 
       Wherein: 
       [0033]    a is 3, 4, 5 or 6; 
         [0034]    L is selected from halogen atom, hydrocarbyl group of C 1 -C 30 , group containing oxygen atom, group containing nitrogen atom; each L in the formula may be same or different, and they may link to one another to form bonds or form a ring; 
         [0035]    the halogen atom is F, Cl, Br, or I; 
         [0036]    the group containing oxygen atom selected from alkoxy —OR 23 , tetrahydrofuran or diethyl ether; The group containing nitrogen atom selected from —NR 24 R 25  or —N(O)R 26 R 27 ; 
         [0037]    R 23 -R 27 , respectively, is H, hydrocarbyl group of C 1 -C 30 , or aryl group of C 5 -C 50 ; these groups may be same or different, and R 24  with R 25 , R 26  with R 27  may form a bond or to form a ring; 
         [0038]    M is a transition metal of group 4 to group 6, preferable to titanium, zirconium, chromium, and vanadium. 
         [0039]    Examples of the “metal complex” include titanium compound, zirconium compound, chromium compound, or vanadium compound, where Titanium compound may be tetrahalogenated titanium or tetrahalogenated titanium coordinated with THF or Et 2 O, preferable to TiCl 4 , TiCl 4 (THF) 2 ; or alkoxy trihalogenated titanium, the preferable are Ti(OCH 3 )Cl 3 , Ti(OC 2 H 5 )Cl 3  or Ti(OC 2 H 5 )Br 3 ; or alkoxy dihalogenated titanium, the preferable are Ti(OCH 3 ) 2 Cl 2 , Ti(OC 2 H 5 ) 2 Cl 2 ; or alkoxy halogenated titanium, preferable to Ti(OCH 3 ) 3 Cl, Ti(OC 2 H 5 ) 3 Cl; or tetraalkoxy titanium, tetraamido titanium or tetraalkyl titanium; Zirconium compound prefer ZrCl 4  or tetraamido zirconium; Chromium compound prefer CrCl 3  or CrCl 3 (THF) 3 ; Vanadium compound is VCl 5 , VCl 3 (THF) 3  or VCl 3 (PMe) 3 . The more preferable “metal complex” is TiCl 4 , TiCl 4 (THF) 2 , Ti(NMe 2 ) 4 , Ti(NEt 2 ) 4 , Ti(CH 2 Ph) 4 , ZrCl 4 , Zr(NMe 2 ) 4 , Zr(NEt 2 ) 4 , CrCl 3 , CrCl 3 (THF) 3 , VCl 3 , or VCl 3 (THF) 3 . The most preferable “metal complex” is TiCl 4 , TiCl 4 (THF) 2 , Ti(CH 2 Ph) 4 , ZrCl 4 , CrCl 3 , CrCl 3 (THF) 3  or VCl 3 (THF) 3 . 
       Preparation of the Single Site Ziegler-Natta Catalyst 
       [0040]    In the present invention, the organic compound containing heteroatom is used effectively as an electron donor (ED) to prepare a single site Ziegler-Natta catalyst by the following procedure: 
         [0041]    (1) pretreating an organic or an inorganic solid or a mixture of them by heating; 
         [0042]    (2) dissolving magnesium compound in THF to form a solution at room temperature to 70° C.; 
         [0043]    (3) to the aforesaid solution (2) was added the pretreated solid (supporter), metal complex and the electron donor, the resulting mixture was kept for several hours under certain temperature, and then removing the solvent, and the residue was washed with inert hydrocarbon solvent and was dried under reduced pressure to provide single-site Ziegler-Natta catalyst. 
         [0044]    In step (1), the solid, which is used as a supporter, is treated at 30-1000° C. for 1-24 hrs under inert atmosphere and reduced pressure; and the optimal supporter is silica with particle size of 1-50 μm, specific surface area of 100-300 m 2 /g, pore volume of 0.5-3 mL/g, and an average pore diameter of 10-50 nm. 
         [0045]    In step (2), the ratio between magnesium compound and THF is 1 g:1-100 mL, preferably 1 g:20-80 mL. 
         [0046]    In step (3), the weight ratio between magnesium compound and supporter is 1:0.1-20, preferably 1:0.5-10; the mole ratio of magnesium compound and metal complex is 0.5-100:1, preferably 0.5-50:1; the mole ratio of electron donor (ED) and metal complex is 0.01-10:1, preferably 0.1-5:1; the reaction temperature is room temperature to 100° C., preferably 50-70° C.; reaction time is 2-48 hrs, preferably 4-24 hrs. 
         [0047]    In step (3), the inert hydrocarbon solvent is hydrocarbon of C 5 -C 10  or arene of C 6 -C 8 , which is selected from pentane, hexane, decane, heptane, octane or toluene, preferably hexane or toluene. 
         [0048]    In step (3), it is workable to treat magnesium compound with metal complex for 2-48 hrs at room temperature to 100° C. first, then with the pretreated supporter, and finally with electron donor for 2-48 hrs at room temperature to 100° C. After removing the solvent, the residue was washed with inert hydrocarbon solvent and dried to provide Ziegler-Natta catalyst; the procedure can also be carried out by the following sequence: treating magnesium compound with a supporter for 2-48 hrs at room temperature to 100° C. to get a composite supporter which then react with a solution of an electronic donor and metal complex for 2-48 hrs at room temperature to 100° C., and by the same treatment mentioned above to provide the desired catalyst. 
         [0049]    In the present invention, the solvents used during preparing single site Ziegler-Natta catalyst are treated to remove water and oxygen strictly and all manipulations were performed under inert atmosphere using standard Schlenk techniques which would not be described again in the following examples. 
         [0050]    The catalyst in the present invention is suitable for ethylene polymerization, ethylene/α-olefin copolymerization, and ethylene/cycloolefin copolymerization. Alkyl aluminum, alkyl aluminoxane, or a mixture of two or more of them is used as cocatalyst in the polymerization process. A suitable cocatalyst selected from AlEt 3 , Al(i-Bu) 3 , AlEt 2 Cl, Al(n-Hex) 3 , MAO, EAO, MMAO, or a mixture of two or more of them, preferably AlEt 3 , MMAO; the suitable mole ratio of Al/Ti is 20-1000, preferably 20-500; the useful α-olefins in the invention are C 3 -C 20  such as propene, 1-butene, 1-hexene, 1-octene, 1-heptene, 4-methyl-1-petene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene; the cycloolefins are cyclopetene, cyclohexene, norbornene or their derivatives. Either α-olefins and cycloolefins used in the present polymerization can be substituted by hydroxyl group, carboxyl group, ester group, or amine group. 
         [0051]    The polymerization can be run in slurry process or gas process. 
         [0052]    In the case of slurry polymerization process, the polymerization is generally performed at 80-120° C. under a total pressure of 0.1-10 MPa with 0-1.0 MPa hydrogen pressure; the polymerization may be carried out under supercritical or subcritical state with inert solvent such as propane, isobutane or hexane as solvent; both autoclave and loop reactor are useful. 
         [0053]    In the case of gas polymerization process, the polymerization is generally conducted under a total pressure of 0.1-10 MPa at 40-100° C. in gas fluidized bed or gas autoclave. 
         [0054]    The metal mass content of the produced single-site Ziegler-Natta catalyst is measured by ICP-AES, OPTRMA-3000 inductively coupled plasma atomic emission spectrometry. 
         [0055]    Molecular weight and molecular weight distribution of the polymers are determined by Waters Alliance GPC2000 (differential refractive index detector) at 135° C. and 1,2,4-trichlorobenzene as eluent, polystyrene as a reference sample. 
         [0056]    The  13 C NMR of the polymer was determined by Varian XL-300 MHz nuclear magnetic resonance spectrometer at 110° C. in d 4 -o-dichlorobenzene. And the incorporation of the comonomer is calculated by the literature method (J. C. Randall,  JMS - Rev. Maromol. Chem. Phys.  1989, C29(2&amp;3), 201-317). 
     
    
     
       BRIEF DESCRIPTION OF THE FIGURES 
         [0057]      FIG. 1  is the X-ray of compound ED14 in example 9. 
           [0058]      FIG. 2  is the  13 C NMR of the ethylene/1-hexene copolymer in example 78. 
       
    
    
     EXAMPLES 
     Example 1 
     Synthesis of Electron Donor (ED) 
       [0059]    
       
                 
         
             
             
         
       
     
         [0060]    To a solution of 1-phenyl-1,3-butanedione (42.0 mmol) and 2-phenoxybenzenamine (40.0 mmol) in anhydrous ethanol (30 mL) was added acetic acid (3 mL). After refluxing for 30 hrs, the resulting mixture was cooled to 0° C. and filtered, the solid was washed with cool ethanol and dried to give ED01 as yellow solid. Yield 5.534 g (42%). ED01:  1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 12.82 (s, 1H), 7.87-7.84 (m, 2H), 7.44-6.91 (m, 12H), 5.86 (s, 1H), 2.12 (s, 3H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 188.83, 162.14, 155.35, 150.68, 139.91, 130.85, 130.29, 129.68, 128.52, 128.18, 127.06, 127.01, 126.87, 124.03, 119.77, 119.53, 94.65, 20.34. 
       Example 2-7 
     Examples 2-7 Provide Some Examples of the Prepared Electron Donor (ED) 
       [0061]    The same procedure as that for the preparation of ED01 was used. These compounds were prepared with the corresponding diketone derivatives and amine derivatives. The characterization data of the ED are showed as following: 
       Example 2 
       [0062]    ED02:  1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 13.02 (s, 1H), 7.94-7.91 (m, 2H), 7.44-6.98 (m, 9H), 6.45-6.42 (m, 1H), 5.96 (s, 1H), 2.34 (s, 3H), 2.15 (s, 6H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 188.76, 162.72, 151.32, 151.06, 140.11, 131.22, 130.73, 128.99, 128.16, 127.36, 127.09, 126.91, 126.44, 125.25, 121.29, 113.45, 94.43, 20.48, 16.32. 
       Example 3 
       [0063]    ED05:  1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 12.82 (s, 1H), 7.88-7.85 (m, 2H), 7.44-6.86 (m, 11H), 5.87 (s, 1H), 2.13 (s, 3H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 188.86, 162.13, 155.96, 150.53, 139.91, 132.63, 130.85, 130.38, 128.19, 127.07, 127.02, 126.89, 124.13, 120.13, 119.69, 115.97, 94.68, 20.32. 
       Example 4 
       [0064]    ED06:  1 H NMR (300 MHz, CDCl 3 ): δ 12.82 (s, 1H), 7.88-7.84 (m, 2H), 7.42-7.38 (m, 5H), 7.10-6.84 (m, 6H), 5.86 (s, 1H), 3.72 (s, 3H), 2.09 (s, 3H). 
       Example 5 
       [0065]    ED07:  1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 12.84 (s, 1H), 7.89-7.86 (m, 2H), 7.43-6.93 (m, 11H), 5.87 (s, 1H), 2.15 (s, 3H), 1.28 (s, 9H). 
       Example 6 
       [0066]    ED08:  1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 12.91 (s, 1H), 7.85-7.79 (m, 5H), 7.42-7.26 (m, 11H), 5.85 (s, 1H), 2.17 (s, 3H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 188.72, 162.35, 154.31, 151.14, 139.97, 134.14, 130.73, 130.29, 130.15, 129.91, 128.12, 127.69, 127.09, 127.04, 126.96, 126.82, 126.47, 124.77, 123.63, 119.78, 119.41, 114.20, 94.58, 20.37. 
       Example 7 
       [0067]    ED09:  1 H NMR (300 MHz, CDCl 3 ): δ 12.82 (s, 1H), 7.95-7.91 (m, 2H), 7.41-7.14 (m, 7H), 5.92 (s, 1H), 3.64 (s, 3H), 2.06 (s, 3H). 
       Example 8 
       [0068]    To a solution of 1-phenyl-1,3-butanedione (10.0 mmol) in CH 3 OH (15 mL) was added 2-(phenylthio)benzenamine (10.0 mmol), and then was added formic acid (0.5 mL). After refluxing for 48 hrs, solvent was removed and the residue was cooled. The generated solid was collected and recrystallized from ethanol and dried to give ED13. Yield 1.8156 g (53%).  1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 12.93 (s, 1H), 7.94-7.91 (m, 2H), 7.47-7.38 (m, 5H), 7.31-7.15 (m, 7H), 5.85 (s, 1H), 1.97 (s, 3H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) δ 188.84, 162.06, 139.94, 137.78, 133.95, 133.52, 132.55, 131.20, 130.83, 129.25, 127.78, 127.22, 127.14, 126.99, 126.88, 94.32, 20.06,. IR: 3060, 1597, 1574, 1546, 1508, 1462, 1425, 1317, 1287, 1271, 1060, 760, 747, 732 cm −1 ; LRMS-EI(m/z): 345 (M + ), 91 (100); elemental analysis for C 22 H 19 NOS: C, 76.64; H, 5.63; N, 3.77. 
       Example 9 
       [0069]    To a solution of 1-phenyl-1,3-butanedione (1.92 mmol) in anhydrous C 2 H 5 OH (7 mL) was added 2-(2,6-dimethylphenylthio)benzenamine (1.74 mmol), and then was added acetic acid (0.6 mL). After refluxing for 24 hrs, solvent was removed and the residue was cooled. The generated solid was collected and recrystallized from ethanol and dried to give ED14. Yield 0.4657 g (72%)  1 H NMR (300 MHz, CDCl 3 ): δ 12.84 (s, 1H), 7.99-7.96 (m, 2H), 7.46-7.43 (m, 3H), 7.25-7.01 (m, 6H), 6.46-6.43 (m, 1H), 5.99 (s, 1H), 2.40 (s, 6H), 2.06 (s, 3H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 188.93, 163.21, 144.06, 139.91, 136.21, 135.14, 130.83, 129.45, 129.17, 128.54, 128.15, 127.50, 127.15, 124.86, 124.76, 93.95, 21.68, 20.01; IR: 3450, 3060, 2920, 1599, 1577, 1550, 1461, 1317, 1284, 747 cm −1 ; LRMS-EI(m/z): 373 (M + ), 105 (100); elemental analysis for C 24 H 23 NOS: C, 77.44; H, 6.18; N, 3.34. Molecular structure of ED14 is showed in  FIG. 1 . 
       Example 10 
       [0070]    To a solution of 1-phenyl-1,3-butanedione (1.16 mmol) in anhydrous C 2 H 5 OH (7 mL) was added 2-(2,6-diisopropylphenylthio)benzenamine (1.05 mmol), and then was added formic acid (0.2 mL). After refluxing for 8 hrs, solvent was removed and the residue was cooled. The generated solid was collected and recrystallized from ethanol and dried to give ED15 (0.3203 g, 71%):  1 H NMR (300 MHz, CDCl 3 ): δ 12.82 (s, 1H), 8.00-7.97 (m, 2H), 7.48-7.01 (m, 9H), 6.40-6.37 (m, 2H), 6.02 (s, 1H), 2.08 (s, 3H), 1.15-1.12 (d, 0.1=7.2 Hz, 12H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 188.98, 154.22, 139.96, 138.55, 130.87, 130.45, 128.22, 127.57, 127.50, 127.20, 126.78, 125.34, 124.55, 124.24, 93.89, 31.66, 24.17, 19.96; IR: 3060, 2960, 1597, 1557, 1461, 1319, 1284, 745 cm −1 ; LRMS-EI (m/z): 430 (M + ), 252 (100); elemental analysis for C 28 H 31 NOS: C, 78.29; H, 7.51; N, 3.07. 
       Example 11 
       [0071]    To a solution of 1-phenyl-1,3-butanedione (1.22 mmol) in anhydrous C 2 H 5 OH (10 mL) was added 2-(2,6-dichlorophenylthio)benzenamine (1.11 mmol), and then was added formic acid (0.5 mL). After refluxing for 20 hrs, solvent was removed and the residue was cooled. The generated solid was collected and recrystallized from ethanol and dried to give ED16 (0.3363 g, 73%):  1 H NMR (300 MHz, CDCl 3 ): δ 12.81 (s, 1H), 7.97-7.94 (m, 2H), 7.47-7.10 (m, 8H), 6.73-6.70 (m, 1H), 5.96 (s, 1H), 2.06 (s, 3H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 189.00, 163.02, 141.70, 139.87, 136.02, 134.02, 130.86, 130.83, 130.29, 128.95, 128.17, 127.84, 127.57, 127.18, 126.83, 126.22, 94.16, 20.08; IR: 3420, 3060, 1600, 1578, 1553, 1426, 1317, 1283, 782, 750 cm −1 ; LRMS-EI (m/z): 414 (M + ), 105 (100); elemental analysis for C 22 H 17 Cl 2 NOS: C, 63.54; H, 4.04; N, 3.20. 
       Example 12-15 
       [0072]    ED17-ED22 were prepared from the corresponding diketone derivatives and amine following the procedure of Example 11: 
         [0073]    ED17:  1 H NMR (300 MHz, CDCl 3 ): δ 12.95 (s, 1H), 7.91-7.88 (m, 2H), 7.47-7.15 (m, 1H), 5.81 (s, 1H), 1.95 (s, 3H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 189.00, 161.53, 139.83, 138.97, 136.57, 134.73, 132.99, 131.35, 130.89, 130.69, 130.08, 129.32, 128.44, 128.15, 127.39, 127.12, 126.99, 126.83, 94.59, 19.99. 
       Example 13 
       [0074]    ED18:  1 H NMR (300 MHz, CDCl 3 ): δ 12.89 (s, 1H), 7.97-7.94 (m, 2H), 7.44-7.40 (m, 5H), 7.13-6.86 (m, 6H), 5.91 (s, 1H), 3.80 (s, 3H), 1.99 (s, 3H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 188.83, 162.59, 160.10, 139.92, 136.71, 136.21, 136.02, 130.85, 128.51, 128.18, 127.17, 127.03, 125.96, 122.36, 115.06, 109.71, 94.10, 55.32, 20.120 
       Example 14 
       [0075]    ED21:  1 H NMR (300 MHz, CDCl 3 ): δ 12.86 (s, 1H), 7.95-7.92 (m, 2H), 7.48-7.20 (m, 7H), 5.95 (s, 1H), 2.00 (s, 3H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 189.28, 162.20, 139.60, 138.08, 131.07, 130.53, 128.42, 128.25, 128.06, 127.61, 127.15, 94.40, 19.96. 
       Example 15 
       [0076]    ED22:  1 H NMR (300 MHz, CDCl 3 ): δ 12.82 (s, 1H), 7.94-7.90 (m, 2H), 7.41-7.13 (m, 7H), 5.91 (s, 1H), 2.47 (s, 3H), 2.04 (s, 3H 
       Example 16 
       [0077]    To a solution of benzoyl acetone (5.54 mmol) in anhydrous C 2 H 5 OH (5 mL) was added 1-(phenylthio)propan-2-amine (5.54 mmol), and then was added formic acid (0.5 mL). After refluxing for 36 hrs, solvent was removed and the residue was cooled. The generated solid was collected and recrystallized from ethanol and dried to give ED23 (1.7245 g, 68%).  1 H NMR (300 MHz, CDCl 3 ): δ 12.86 (s, 1H), 7.96-7.94 (m, 2H), 7.46-7.17 (m, 7H), 5.94 (s, 1H), 2.89-2.84 (t, J=7.2 Hz, 2H), 2.04 (s, 3H), 1.71-1.64 (m, 2H), 1.05-1.00 (t, J=7.5 Hz, 3H).  13 C NMR (75 MHz, CDCl 3 ): 188.83, 162.45, 139.97, 137.53, 134.23, 130.83, 128.83, 128.17, 127.19, 126.85, 126.75, 125.89, 94.21, 34.64, 22.28, 20.23, 13.52; IR: 3060, 2962, 1598, 1574, 1548, 1515, 1461, 1432, 1317, 1280, 1195, 1064, 754, 708 cm −1 ; LRMS-EI(m/z): 311 (M + ), 105 (100); elemental analysis for C 19 H 21 NOS: C, 73.20; H, 6.81; N, 4.23. 
       Example 17-20 
       [0078]    ED24-ED27 were prepared from the corresponding diketone derivatives and amine following the procedure of example 16: 
       Example 17 
       [0079]    ED24:  1 H NMR (300 MHz, CDCl 3 ): δ 12.94 (s, 1H), 7.97-7.93 (m, 2H), 7.49-7.17 (m, 7H), 5.93 (s, 1H), 3.41-3.37 (m, 1H), 2.07 (s, 3H), 1.31-1.29 (d, J=6 Hz, 6H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 188.67, 161.81, 139.95, 139.17, 132.57, 131.96, 130.75, 128.11, 127.10, 126.34, 126.20, 94.43, 37.50, 22.91, 20.34; IR: 3060, 2980, 1598, 1577, 1511, 1436, 1320, 1280, 758, 703, 673 cm −1 ; LRMS-EI(m/z): 311 (M + ), 105 (100); elemental analysis for C 19 H 21 NOS: C, 73.19; H, 6.74; N, 4.14. 
       Example 18 
       [0080]    ED25:  1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 13.17 (s, 1H), 7.98-7.94 (m, 2H), 7.66-7.63 (m, 1H), 7.47-7.17 (m, 6H), 5.93 (s, 1H), 2.14 (s, 3H), 1.32 (s, 9H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 188.53, 160.52, 143.05, 139.82, 130.80, 129.64, 128.16, 127.20, 125.20, 125.02, 95.17, 47.86, 30.84, 20.82; IR: 3060, 2980, 1596, 1577, 1555, 1456, 1321, 1280, 759 cm −1 ; LRMS-EI(m/z): 325 (M + ), 105 (100); elemental analysis for C 20 H 23 NOS: C, 73.73; H, 7.07; N, 3.95. 
       Example 19 
       [0081]    ED26:  1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 12.35 (s, 1H), 7.34-7.17 (m, 8H), 5.44 (s, 1H), 1.91 (s, 3H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 176.53, 167.93, 136.39, 134.25, 132.97, 132.34, 131.83, 129.41, 128.30, 128.09, 127.70, 127.25, 115.47, 90.81 (t), 19.92; IR: 3155, 2925, 2852, 1620, 1590, 1565, 1467, 1439, 1428, 1292, 1241, 1062, 861, 753, 745, 734 cm −1 ; elemental analysis for C 17 H 14 F 3 NOS: C, 60.68; H, 4.15; N, 3.95. 
       Example 20 
       [0082]    ED27:  1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 12.91 (s, 1H), 7.99-6.41 (m, 18H), 6.08 (s, 1H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 189.59, 160.50, 139.94, 139.68, 135.87, 134.50, 132.95, 131.91, 131.31, 129.61, 129.12, 128.91, 128.44, 128.27, 128.03, 127.53, 127.41, 127.36, 124.90, 124.46, 97.92; IR: 3051, 1545, 1480, 1438, 1330, 1282, 1207, 1050, 1022, 781, 754, 686 cm −1 ; elemental analysis for C 27 H 21 NOS: C, 79.23; H, 5.18; N, 3.13. 
       Example 21 
       [0083]    To a solution of acetylacetone (10 mmol) in CH 3 OH (15 mL) was added 2-(phenylthio)benzenamine (10 mmol), and then was added formic acid (1 mL). After refluxing for 24 hrs, solvent was removed and the residue was cooled. The generated solid was collected and recrystallized from ethanol and dried to give ED28 (1.8156 g, 52.6%).  1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 12.34 (s, 1H), 7.35-7.26 (m, 5H), 7.19-7.11 (m, 4H), 5.15 (s, 1H), 2.09 (s, 3H), 1.84 (s, 3H);  13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 196.30, 159.95, 137.83, 133.68, 132.36, 131.14, 129.20, 128.92, 127.71, 127.17, 126.85, 126.66, 126.33, 97.77, 29.15, 19.49. IR: 3058, 1575, 1500, 1462, 1439, 1377, 1355, 1275, 1186, 1063, 1024, 993, 921, 751, 691, 660 cm −1 ; LRMS-EI(m/z): 283 (M + ), 174 (100); elemental analysis for C 17 H 17 NOS: C, 72.09; H, 6.02; N, 4.78. 
       Example 22-31 
       [0084]    ED33-44 were prepared following the procedure showed in example 21. 
       Example 22 
       [0085]    ED33:  1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 12.90 (s, 1H), 7.93-7.14 (m, 19H), 5.81 (s, 1H), 1.94 (s, 3H). 
       Example 23 
       [0086]    ED35:  1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 12.87 (s, 1H), 7.95-7.11 (m, 24H), 6.35 (s, 1H). 
       Example 24 
       [0087]    ED37:  1 H NMR (300 MHz, CDCl 3 ): δ 13.08 (s, 1H), 7.81-7.49 (m, 5H), 5.77 (s, 1H), 3.02 (t, 2H), 2.70 (t, 2H), 2.09 (s, 3H), 1.96 (t, 3H). 
       Example 25 
       [0088]    ED38:  1 H NMR (300 MHz, CDCl 3 ): δ 13.28 (s, 1H), 7.81-7.49 (m, 5H), 5.77 (s, 1H), 3.02 (t, 2H), 2.88 (m, 1H), 2.70 (t, 2H), 1.95 (t, 3H), 1.25 (d, 6H). 
       Example 26 
       [0089]    ED39:  1 H NMR (300 MHz, CDCl 3 ): δ 12.38 (s, 1H), 7.81-6.56 (m, 16H), 5.99 (s, 1H), 1.71 (t, 3H). 
       Example 27 
       [0090]    ED40:  1 H NMR (300 MHz, CDCl 3 ): δ 12.38 (s, 1H), 7.81-7.49 (m, 5H), 7.44-7.22 (m, 5H), 6.75-6.14 (m, 3H), 5.99 (s, 1H), 2.35 (s, 3H), 1.71 (s, 3H). 
       Example 28 
       [0091]    ED41:  1 H NMR (300 MHz, CDCl 3 ): δ 12.89 (s, 1H), 7.97-7.64 (m, 5H), 7.44-7.22 (m, 5H), 6.66-6.24 (m, 3H), 5.95 (s, 1H), 1.91 (s, 3H). 
       Example 29 
       [0092]    ED42:  1 H NMR (300 MHz, CDCl 3 ): δ 12.38 (s, 1H), 9.77 (s, 1H), 7.81-7.49 (m, 5H), 7.33-6.98 (m, 5H), 6.61-6.21 (m, 4H), 5.99 (s, 1H), 1.71 (s, 3H). 
       Example 30 
       [0093]    ED43:  1 H NMR (300 MHz, CDCl 3 ): δ 12.38 (s, 1H), 8.80 (s, 1H), 7.94-6.84 (m, 10H), 5.97 (s, 1H), 1.73 (s, 3H). 
       Example 31 
       [0094]    ED44:  1 H NMR (300 MHz, CDCl 3 ): δ 12.40 (s, 1H), 7.98-6.39 (m, 12H), 5.95 (s, 1H), 1.75 (s, 3H). 
       Example 32 
       [0095]    The synthesis of single site Ziegler-Natta catalyst In the present invention: 
         [0000]    (1) Thermo-pretreatment of the supporter
 
ES70 silica (product of Ineos company) is calcinated under nitrogen atmosphere at 200° C. for 2 hrs and then for 4 hrs at 400° C., after that it is cooled under nitrogen atmosphere to provide supporter ES70.
 
(2) the synthesis of single-site Ziegler-Natta catalyst
 
       Method One: 
       [0096]    A solution of anhydrous MgCl 2  (1.0 g) in tetrahydrofuran (THF for short, 40 mL) was stirred at 60° C. for 2 h; then to the solution was added TiCl 4  (3.4 mmol) and the reaction mixture was heated at 60° C. for 4 h. Then the pretreated ES70 supporter (1.0 g) was added and the resulting mixture was heated for further 4 hrs at 60° C. To the mixture was added desired electron donor and the reaction system was maintained at 60° C. for another 12 hrs. Then, the solvent was removed under reduced atmosphere, and the residue was washed with hexane (3×20 mL) and then dried under vacuum to provide a fluid brown powder. Ti content: 3.20 wt-%. 
       Method Two: 
       [0097]    To tetrahydrofuran (THF for short, 40 mL) was added anhydrous MgCl 2  (1.0 g) and the resulting suspension was stirred for 2 hrs at 60° C. to get MgCl 2  dissolved totally. To the resulting solution was added silica (1.7 g) and the mixture was stirred for 1 h. Hexane (40 mL) was added and then the reaction system was cooled to room temperature under stirring. After filtration, the obtained solid was dried under vacuum to provide a composite supporter. 
         [0098]    To a solution of TiCl 4 (THF) 2  in dichloromethane (2 mL) was added a solution of electronic donor ED01 in dichloromethane (2 mL), and the resulting solution was added to the composite supporter (0.77 g) with stifling. Removing the solvent under vacuum to provide Ziegler-Natta catalyst as fluid brown powders. 
       Example 33-69 
       [0099]    The following examples are the synthesis of the Ziegler-Natta catalyst according to the same procedure of example 32 (Table 1). 
         [0000]    
       
         
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                   
                   
                 Anhydrous 
                 THF 
                 TiCl 4   
                 supporter 
                   
                 Ti 
               
               
                 Example 
                 Catalyst 
                 MgCl 2  (g) 
                 (mL) 
                 (mmol) 
                 (g) 
                 ED (mmol) 
                 (wt-%) 
               
               
                   
               
             
             
               
                 33 
                 SC02 
                 1.0 
                 40 
                 3.4 
                 ES70(1.0) 
                 ED02(3.5) 
                 4.61 
               
               
                 34 
                 SC03 
                 1.0 
                 40 
                 3.4 
                 ES757(1.0) 
                 ED02(3.5) 
                 4.56 
               
               
                 35 
                 SC04 
                 1.0 
                 40 
                 3.4 
                 Grace955(1.0) 
                 ED02(3.5) 
                 — 
               
               
                 36 
                 SC05 
                 1.2 
                 50 
                 3.4 
                 ES70(1.0) 
                 ED05(3.5) 
                 4.35 
               
               
                 37 
                 SC06 
                 1.2 
                 50 
                 3.4 
                 ES70(1.0) 
                 ED06(4.0) 
                 — 
               
               
                 38 
                 SC07 
                 0.9 
                 40 
                 3.4 
                 ES70X(1.0) 
                 ED07(6.8) 
                 3.75 
               
               
                 39 
                 SC08 
                 1.2 
                 50 
                 3.4 
                 ES70Y(1.1) 
                 ED08(4.0) 
                 — 
               
               
                 40 
                 SC09 
                 1.0 
                 40 
                 3.4 
                 ES70(1.0) 
                 ED09(4.0) 
                 4.65 
               
               
                 41 
                 SC11 
                 1.0 
                 40 
                 3.4 
                 ES70(1.0) 
                 ED13(4.1) 
                 4.50 
               
               
                 42 
                 SC12 
                 1.1 
                 40 
                 1.7 
                 ES70(1.3) 
                 ED13(3.4) 
                 1.68 
               
               
                 43 
                 SC13 
                 0.5 
                 20 
                 3.4 
                 ES70(1.0) 
                 ED13(4.1) 
                 1.09 
               
               
                 44 
                 SC14 
                 1.0 
                 60 
                 6.8 
                 ES70(2.0) 
                 ED13(8.2) 
                 5.65 
               
               
                 45 
                 SC15 
                 1.0 
                 40 
                 3.0 
                 ES70(1.0) 
                 ED13(1.5) 
                 4.59 
               
               
                 46 
                 SC16 
                 2.0 
                 60 
                 3.2 
                 ES757(2.0) 
                 ED13(3.8) 
                 — 
               
               
                 47 
                 SC17 
                 0.5 
                 30 
                 1.7 
                 ES70(0.5) 
                 ED14(2.6) 
                 — 
               
               
                 48 
                 SC18 
                 0.5 
                 30 
                 1.7 
                 ES70(0.5) 
                 ED15(2.6) 
                 4.45 
               
               
                 49 
                 SC19 
                 0.5 
                 30 
                 1.7 
                 ES70(0.5) 
                 ED16(2.6) 
                 — 
               
               
                 50 
                 SC20 
                 0.5 
                 30 
                 1.7 
                 ES70(0.5) 
                 ED17(2.6) 
                 4.35 
               
               
                 51 
                 SC21 
                 0.5 
                 30 
                 1.7 
                 ES70(0.5) 
                 ED18(2.6) 
                 4.37 
               
               
                 52 
                 SC22 
                 0.5 
                 30 
                 1.7 
                 ES70(0.5) 
                 ED21(2.6) 
                 3.95 
               
               
                 53 
                 SC23 
                 0.5 
                 30 
                 1.7 
                 ES70(0.5) 
                 ED22(2.6) 
                 — 
               
               
                 54 
                 SC24 
                 0.5 
                 30 
                 1.7 
                 ES70(0.5) 
                 ED23(2.6) 
                 4.43 
               
               
                 55 
                 SC25 
                 0.5 
                 30 
                 1.7 
                 ES70(0.5) 
                 ED24(2.6) 
                 — 
               
               
                 56 
                 SC26 
                 0.5 
                 30 
                 1.7 
                 ES70(0.5) 
                 ED25(2.6) 
                 4.53 
               
               
                 57 
                 SC27 
                 1.0 
                 60 
                 6.8 
                 ES70(2.0) 
                 ED26(8.2) 
                 — 
               
               
                 58 
                 SC28 
                 1.0 
                 60 
                 6.8 
                 ES757(2.0) 
                 ED27(8.2) 
                 — 
               
               
                 59 
                 SC29 
                 1.0 
                 60 
                 6.8 
                 ES70(2.0) 
                 ED28(8.2) 
                 — 
               
               
                 60 
                 SC30 
                 1.0 
                 60 
                 0.8 
                 ES70(2.0) 
                 ED33(1.8) 
                 0.82 
               
               
                 61 
                 SC31 
                 0.5 
                 60 
                 0.8 
                 ES757(3.0) 
                 ED35(1.6) 
                 0.40 
               
               
                 62 
                 SC32 
                 1.0 
                 40 
                 3.4 
                 ES70(1.0) 
                 ED37(4.1) 
                 — 
               
               
                 63 
                 SC33 
                 1.0 
                 40 
                 3.4 
                 ES70(1.0) 
                 ED38(4.1) 
                 — 
               
               
                 64 
                 SC34 
                 1.0 
                 40 
                 3.4 
                 ES70(1.0) 
                 ED39(4.1) 
                 — 
               
               
                 65 
                 SC35 
                 1.0 
                 40 
                 3.4 
                 ES70(1.0) 
                 ED40(4.1) 
                 — 
               
               
                 66 
                 SC36 
                 1.0 
                 40 
                 3.4 
                 ES70(1.0) 
                 ED41(4.1) 
                 — 
               
               
                 67 
                 SC37 
                 1.0 
                 40 
                 3.4 
                 ES70(1.0) 
                 ED42(4.1) 
                 4.10 
               
               
                 68 
                 SC38 
                 1.0 
                 40 
                 3.4 
                 ES70(1.0) 
                 ED43(4.1) 
                 3.67 
               
               
                 69 
                 SC39 
                 1.0 
                 40 
                 3.4 
                 ES70(1.0) 
                 ED44(4.1) 
                 — 
               
               
                   
               
             
          
         
       
     
       Example 70-74 
       [0100]    The following examples are synthesis of the Ziegler-Natta catalyst containing electron donor according to the same procedure of example 32 (Table 2). 
         [0000]    
       
         
               
               
               
               
               
             
           
               
                 TABLE 2 
               
               
                   
               
               
                   
                 Catalyst 
                   
                 electronic 
                 Metal content 
               
               
                 example 
                 number 
                 Metal complex 
                 donor (mmol) 
                 (wt-%) 
               
               
                   
               
             
             
               
                 70 
                 SC40 
                 TiCl 4 (THF) 2   
                 ED13(3.5) 
                 4.42 
               
               
                 71 
                 SC41 
                 ZrCl 4   
                 ED13(3.5) 
                 3.36 
               
               
                 72 
                 SC42 
                 CrCl 3   
                 ED27(3.5) 
                 — 
               
               
                 73 
                 SC43 
                 CrCl 3 (THF) 3   
                 ED33(3.5) 
                 3.41 
               
               
                 74 
                 SC44 
                 VCl 3 (THF) 3   
                 ED35(4.0) 
                 — 
               
               
                   
               
             
          
         
       
     
       Example 75-103 
       [0101]    The following examples are ethylene polymerization by slurry process: A 500 mL stainless-steel autoclave equipped with mechanical stirrer was dried under vacuum and then purged with nitrogen for three times and with ethylene for two times. Freshly distilled 180 g n-hexane (200 mL n-hexane+1.0 mL AlEt 3  (3.0 M in hexane)) was transferred to the reactor and the solution was stirred (rotate speed=150 rpm) at 60° C. Under nitrogen atmosphere, desired amount of comonomer (in the case of the copolymerization) and Ziegler-Natta catalyst (10 mg) were added in order then the pressure in autoclave was released. Raising the temperature of the solution to 80° C., and then ethylene gas was fed to get the pressure of autoclave to 1.0 MPa. After 5 min, the rotate speed was raised to 250 rpm and the temperature of water bath was raised to 85° C. for 1 h. The autoclave was cooled quickly to below 50° C., and the product was dried to get polymer as particle. 
         [0102]    The detailed experimental conditions, catalytic activity (g polymer/g catalyst), polymer molecular weight M w  (g/mol), polymer molecular weight distribution (PDI) and the polymer bulk density (g/cm 3 ), etc. were listed in Table 3. The  13 C NMR of the ethylene/1-hexene copolymer obtained in example 78 was showed in  FIG. 2 . 
         [0000]    
       
         
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                 Comonomer 
               
               
                   
                   
                   
                 Comonomer 
                 Activity 
                 M w   
                   
                 incorporation 
               
               
                 Example 
                 Catalyst 
                 Comonomer 
                 loading (g) 
                 (g/g) 
                 (10 4  g/mol) 
                 PDI 
                 (mol-%) 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 75 
                 SC01 
                 — 
                 0 
                 1000 
                 11.6 
                 3.46 
                 — 
               
               
                 76 
                 SC02 
                 — 
                 0 
                 930 
                 12.7 
                 3.35 
                 — 
               
               
                 77 
                 SC03 
                 1-hexene 
                 10 
                 1500 
                 10.8 
                 3.52 
                 2.05 
               
               
                 78 
                 SC04 
                 1-hexene 
                 20 
                 1200 
                 10.3 
                 3.56 
                 1.04 
               
               
                 79 
                 SC05 
                 — 
                 0 
                 850 
                 — 
                 — 
                 — 
               
               
                 80 
                 SC06 
                 — 
                 0 
                 1100 
                 — 
                 — 
                 — 
               
               
                 81 
                 SC07 
                 — 
                 0 
                 1140 
                 — 
                 — 
                 — 
               
               
                 82 
                 SC08 
                 — 
                 0 
                 740 
                 — 
                 — 
                 — 
               
               
                 83 
                 SC09 
                 1-hexene 
                 10 
                 1360 
                 10.5 
                   
                 1.95 
               
               
                 84 
                 SC18 
                 — 
                 0 
                 2000 
                 16.7 
                 2.45 
                 — 
               
               
                 85 
                 SC19 
                 — 
                 0 
                 900 
                 18.5 
                 3.25 
                 — 
               
               
                 86 
                 SC20 
                 — 
                 0 
                 3500 
                 12.3 
                 3.22 
                 — 
               
               
                 87 
                 SC21 
                 — 
                 0 
                 1500 
                 19.4 
                 3.07 
                 — 
               
               
                 88 
                 SC22 
                 1-hexene 
                 10 
                 1840 
                 15.2 
                 3.20 
                 2.03 
               
               
                 89 
                 SC25 
                 1-hexene 
                 10 
                 4200 
                 14.5 
                 3.41 
                 1.68 
               
               
                 90 
                 SC26 
                 1-hexene 
                 10 
                 3700 
                 13.8 
                 3.35 
                 1.81 
               
               
                 91 
                 SC32 
                 — 
                 0 
                 1660 
                 14.0 
                 3.56 
                 — 
               
               
                 92 
                 SC33 
                 — 
                 0 
                 1200 
                 11.2 
                 1.81 
                 — 
               
               
                 93 
                 SC34 
                 — 
                 0 
                 1500 
                  1.3 
                 3.20 
                 — 
               
               
                 94 
                 SC35 
                 — 
                 0 
                 1430 
                  1.5 
                 3.11 
                 — 
               
               
                 95 
                 SC36 
                 — 
                 0 
                 1700 
                 10.3 
                 3.69 
                 — 
               
               
                 96 
                 SC37 
                 — 
                 0 
                 2100 
                 — 
                 — 
                 — 
               
               
                 97 
                 SC38 
                 — 
                 0 
                 1500 
                 — 
                 — 
                 — 
               
               
                 98 
                 SC39 
                 — 
                 0 
                 1250 
                 — 
                 — 
                 — 
               
               
                 99 
                 SC40 
                 — 
                 0 
                 1650 
                 — 
                 — 
                 — 
               
               
                 100 
                 SC41 
                 — 
                 0 
                 860 
                 — 
                 — 
                 — 
               
               
                 101 
                 SC42 
                 — 
                 0 
                 1120 
                 — 
                 — 
                 — 
               
               
                 102 
                 SC43 
                 — 
                 0 
                 1300 
                 — 
                 — 
                 — 
               
               
                 103 
                 SC44 
                 — 
                 0 
                 1000 
                 — 
                 — 
                 — 
               
               
                   
               
             
          
         
       
     
       Example 104-121 
       [0103]    The following examples are ethylene (co)polymerization by slurry process: A 2 L stainless-steel autoclave equipped with mechanical stirrer was dried under vacuum and then purged with nitrogen for three times and with ethylene for two times. Freshly distilled n-hexane (400 g) was transferred to the reactor and then the solution was stirred (rotate speed=150 rpm) at 60° C. Under nitrogen atmosphere, Ziegler-Natta catalyst (30 mg), n-hexane (200 g), and AlEt 3  (2.1 mL, 0.88 M in n-hexane solution) were added to a charging tank and were shaken sufficiently and then the charging tank were connected to the polymerization system. The solution in the charging tank was pressed into autoclave by nitrogen gas, and then the residual pressure in autoclave was released. At 70° C., ethylene gas was fed into the reactor to keep the pressure of the autoclave (the hydrogen has been pumped in first in the case of hydrogen modulation polymerization) to 0.8 MPa. After 5 min, the rotate speed was raised to 250 rpm and the temperature of water bath rose to 85° C. in the case of copolymerization, a certain amount of comonomers was added after the polymerization was ran for 20 min. After 2 h, the autoclave was cooled quickly to below 50° C. The product was vented and dried to get the polymer as particles. 
         [0104]    The detailed experimental condition, catalytic activity (g polymer/g catalyst), polymer molecular weight M w  (g/mol), polymer molecular weight distribution (PDI), and the polymer bulk density (g/cm 3 ), etc. were showed in Table 4. 
         [0000]    
       
         
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
               
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                 Comonomer 
               
               
                   
                   
                   
                 Comonomer 
                 Activity 
                 M w   
                   
                 incorporation 
               
               
                 Example 
                 Catalyst 
                 Comonomer 
                 loading (g) 
                 (g/g) 
                 (10 4  g/mol) 
                 PDI 
                 (mol %) 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 104 
                 SC11 
                 — 
                 0 
                 18000 
                 30.2 
                 2.18 
                 — 
               
               
                 105 
                 SC11 
                 1-butene 
                 30 
                 12500 
                 31.5 
                 2.65 
                 0.15 
               
               
                 106 
                 SC11 
                 1-butene 
                 60 
                 9500 
                 — 
                 — 
                 0.34 
               
               
                 107 
                 SC11 
                 1-hexene 
                 30 
                 11000 
                 19.8 
                 3.66 
                 0.61 
               
               
                 108 
                 SC11 
                 1-hexene 
                 60 
                 7400 
                 — 
                 — 
                 — 
               
               
                 109 
                 SC12 
                 — 
                 0 
                 5300 
                 — 
                 — 
                 — 
               
               
                 110 
                 SC13 
                 — 
                 0 
                 8600 
                 — 
                 — 
                 — 
               
               
                 111 
                 SC15 
                 — 
                 0 
                 12600 
                 25.4 
                 3.12 
                 — 
               
               
                 112 
                 SC15 
                 1-butene 
                 30 
                 10500 
                 19.0 
                 3.45 
                 — 
               
               
                 113 
                 SC15 
                 1-hexene 
                 30 
                 7200 
                 — 
                 — 
                 — 
               
               
                 114 
                 SC15 
                 1-hexene 
                 60 
                 4700 
                 17.6 
                 3.19 
                 0.26 
               
               
                 115 
                 SC17 
                 — 
                 0 
                 16000 
                 — 
                 — 
                 — 
               
               
                 116 
                 SC23 
                 — 
                 0 
                 11600 
                 38.4 
                 2.05 
                 — 
               
               
                 117 
                 SC24 
                 1-hexene 
                 30 
                 12200 
                 20.8 
                 2.46 
                 0.95 
               
               
                 118 
                 SC28 
                 — 
                 0 
                 3400 
                 — 
                 — 
                 — 
               
               
                 119 
                 SC29 
                 1-hexene 
                 30 
                 16300 
                 21.5 
                 2.32 
                 0.87 
               
               
                 120 
                 SC30 
                 — 
                 0 
                 10400 
                 — 
                 — 
                 — 
               
               
                 121 
                 SC31 
                 — 
                 0 
                 12000 
                 — 
                 — 
                 —