Patent Application
20090137383
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.
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.
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; CN 1189487C (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 SiO2 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.
The purpose of the invention is to provide a new class of organic compounds containing heteroatoms.
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.
The purpose of the invention is also to provide a new class of single-site Ziegler-Natta catalysts and their preparation methods.
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 C3-C18, 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).
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.
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 C3-C18, 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.
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:
The organic compounds containing heteroatoms provided in the present invention are showed below:
in the compound, R1 and R2, respectively, is H, hydrocarbyl of C1-C30, substituted hydrocarbyl of C1-C30, aryl group of C5-C50, or substituted aryl group of C5-C50, while these groups may be same or different;
R3, R4, R5, R6, R7, R8, and R9, respectively, is H, hydrocarbyl group of C1-C30, substituted hydrocarbyl group of C1-C30, aryl group of C5-C50, or substituted aryl group of C5-C50, while these groups may be same or different, of which, R4, R5 with R6 or R7, R6 with R8 or R9, R7 with R8 or R9 may form a bond or form a cycle;
X is O, N, S, Se or P;
when X is O, S or Se, there is only one group R8 or R9 on X;
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 —OR10, group containing sulfur atom —SR11 or —S(O)R12, group containing nitrogen atom —NR13R14 or —N(O)R15R16, or group containing phosphorous atom —PR17R18 or —P(O)R19R20, group containing selenium atom —SeR11 or —Se(O)R12;
R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21 or R22 is substituted hydrocarbyl group of C1-C30, aryl group of C5-C50, of them, R13 and R14, R15 and R16, R17 and R18, R19 and R20 can link to one another to form covalent bond or to form a ring;
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:
R1-R9 are the groups as aforementioned.
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:
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.
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).
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).
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;
the molar ratio of diketone, amine, and catalyst is 1-1.5:1:0.01-0.1;
diketone is described by formula (III):
amine can be described by formula (IV):
R1-R9 are the groups as those mentioned above.
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 %.
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.
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 Al2O3, SiO2, or a mixture of two or more metal oxides.
The “metal complex” can be represented by the formula (V):
MLa (V)
a is 3, 4, 5 or 6;
L is selected from halogen atom, hydrocarbyl group of C1-C30, 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;
the halogen atom is F, Cl, Br, or I;
the group containing oxygen atom selected from alkoxy —OR23, tetrahydrofuran or diethyl ether; The group containing nitrogen atom selected from —NR24R25 or —N(O)R26R27;
R23-R27, respectively, is H, hydrocarbyl group of C1-C30, or aryl group of C5-C50; these groups may be same or different, and R24 with R25, R26 with R27 may form a bond or to form a ring;
M is a transition metal of group 4 to group 6, preferable to titanium, zirconium, chromium, and vanadium.
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 Et2O, preferable to TiCl4, TiCl4(THF)2; or alkoxy trihalogenated titanium, the preferable are Ti(OCH3)Cl3, Ti(OC2H5)Cl3 or Ti(OC2Hs)Br3; or alkoxy dihalogenated titanium, the preferable are Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2; or alkoxy halogenated titanium, preferable to Ti(OCH3)3Cl, Ti(OC2Hs)3Cl; or tetraalkoxy titanium, tetraamido titanium or tetraalkyl titanium; Zirconium compound prefer ZrCl4 or tetraamido zirconium; Chromium compound prefer CrCl3 or CrCl3(THF)3; Vanadium compound is VCl5, VCl3(THF)3 or VCl3(PMe)3. The more preferable “metal complex” is TiCl4, TiCl4(THF)2, Ti(NMe2)4, Ti(NEt2)4, Ti(CH2Ph)4, ZrCl4, Zr(NMe2)4, Zr(NEt2)4, CrCl3, CrCl3(THF)3, VCl3, or VCl3(THF)3. The most preferable “metal complex” is TiCl4, TiCl4(THF)2, Ti(CH2Ph)4, ZrCl4, CrCl3, CrCl3(THF)3 or VCl3(THF)3.
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:
(1) pretreating an organic or an inorganic solid or a mixture of them by heating;
(2) dissolving magnesium compound in THF to form a solution at room temperature to 70° C.;
(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.
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 m2/g, pore volume of 0.5-3 mL/g, and an average pore diameter of 10-50 nm.
In step (2), the ratio between magnesium compound and THF is 1 g:1-100 mL, preferably 1 g:20-80 mL.
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.
In step (3), the inert hydrocarbon solvent is hydrocarbon of C5-C10 or arene of C6-C8, which is selected from pentane, hexane, decane, heptane, octane or toluene, preferably hexane or toluene.
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.
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.
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 AlEt3, Al(i-Bu)3, AlEt2Cl, Al(n-Hex)3, MAO, EAO, MMAO, or a mixture of two or more of them, preferably AlEt3, MMAO; the suitable mole ratio of Al/Ti is 20-1000, preferably 20-500; the useful α-olefins in the invention are C3-C20 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.
The polymerization can be run in slurry process or gas process.
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.
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.
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.
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.
The 13C NMR of the polymer was determined by Varian XL-300 MHz nuclear magnetic resonance spectrometer at 110° C. in d4-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&3), 201-317).
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: 1H NMR (300 MHz, CDCl3): 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); 13C NMR (75 MHz, CDCl3): 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.
Examples 2-7 provide some examples of the prepared electron donor (ED)
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:
ED02: 1H NMR (300 MHz, CDCl3): 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); 13C NMR (75 MHz, CDCl3): 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.
ED05: 1H NMR (300 MHz, CDCl3): 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); 13C NMR (75 MHz, CDCl3): 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.
ED06: 1H NMR (300 MHz, CDCl3): 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).
ED07: 1H NMR (300 MHz, CDCl3): 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).
ED08: 1H NMR (300 MHz, CDCl3): 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); 13C NMR (75 MHz, CDCl3): 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.
ED09: 1H NMR (300 MHz, CDCl3): 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).
To a solution of 1-phenyl-1,3-butanedione (10.0 mmol) in CH3OH (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%). 1H NMR (300 MHz, CDCl3): 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); 13C NMR (75 MHz, CDCl3): 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 C22H19NOS: C, 76.64; H, 5.63; N, 3.77.
To a solution of 1-phenyl-1,3-butanedione (1.92 mmol) in anhydrous C2H5OH (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%) 1H NMR (300 MHz, CDCl3): 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); 13C NMR (75 MHz, CDCl3): 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 C24H23NOS: C, 77.44; H, 6.18; N, 3.34. Molecular structure of ED14 is showed in
To a solution of 1-phenyl-1,3-butanedione (1.16 mmol) in anhydrous C2H5OH (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%): 1H NMR (300 MHz, CDCl3): 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, J=7.2 Hz, 12H); 13C NMR (75 MHz, CDCl3): 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 C28H31NOS: C, 78.29; H, 7.51; N, 3.07.
To a solution of 1-phenyl-1,3-butanedione (1.22 mmol) in anhydrous C2H5OH (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%): 1H NMR (300 MHz, CDCl3): 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); 13C NMR (75 MHz, CDCl3): 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 C22H17Cl2NOS: C, 63.54; H, 4.04; N, 3.20.
ED17-ED22 were prepared from the corresponding diketone derivatives and amine following the procedure of Example 11:
ED17: 1H NMR (300 MHz, CDCl3): δ 12.95 (s, 1H), 7.91-7.88 (m, 2H), 7.47-7.15 (m, 11H), 5.81 (s, 1H), 1.95 (s, 3H); 13C NMR (75 MHz, CDCl3): 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.
ED18: 1H NMR (300 MHz, CDCl3): 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); 13C NMR (75 MHz, CDCl3): 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, 20.12.
ED21: 1H NMR (300 MHz, CDCl3): 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); 13C NMR (75 MHz, CDCl3): 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.
ED22: 1H NMR (300 MHz, CDCl3): 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
To a solution of benzoyl acetone (5.54 mmol) in anhydrous C2H5OH (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%). 1H NMR (300 MHz, CDCl3): 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). 13C NMR (75 MHz, CDCl3): 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 C19H21NOS: C, 73.20; H, 6.81; N, 4.23.
ED24-ED27 were prepared from the corresponding diketone derivatives and amine following the procedure of example 16:
ED24: 1H NMR (300 MHz, CDCl3): 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); 13C NMR (75 MHz, CDCl3): 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 C19H21NOS: C, 73.19; H, 6.74; N, 4.14.
ED25: 1H NMR (300 MHz, CDCl3): 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); 13C NMR (75 MHz, CDCl3): 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 C20H23NOS: C, 73.73; H, 7.07; N, 3.95.
ED26: 1H NMR (300 MHz, CDCl3): δ (ppm) 12.35 (s, 1H), 7.34-7.17 (m, 8H), 5.44 (s, 1H), 1.91 (s, 3H); 13C NMR (75 MHz, CDCl3): 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 C17H14F3NOS: C, 60.68; H, 4.15; N, 3.95.
ED27: 1H NMR (300 MHz, CDCl3): δ (ppm) 12.91 (s, 1H), 7.99-6.41 (m, 18H), 6.08 (s, 1H); 13C NMR (75 MHz, CDCl3): 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 C27H21NOS: C, 79.23; H, 5.18; N, 3.13.
To a solution of acetylacetone (10 mmol) in CH3OH (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%). 1H NMR (300 MHz, CDCl3): 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); 13C NMR (75 MHz, CDCl3): 6 (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-ET(m/z): 283 (M+), 174 (100); elemental analysis for C17H17NOS: C, 72.09; H, 6.02; N, 4.78.
ED33-44 were prepared following the procedure showed in example 21.
ED33: 1H NMR (300 MHz, CDCl3): δ (ppm) 12.90 (s, 1H), 7.93-7.14 (m, 19H), 5.81 (s, 1H), 1.94 (s, 3H).
ED35: 1H NMR (300 MHz, CDCl3): δ (ppm) 12.87 (s, 1H), 7.95-7.11 (m, 24H), 6.35 (s, 1H)o
ED37: 1H NMR (300 MHz, CDCl3): 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)o
ED38: 1H NMR (300 MHz, CDCl3): 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)o
ED39: 1H NMR (300 MHz, CDCl3): δ 12.38 (s, 1H), 7.81-6.56 (m, 16H), 5.99 (s, 1H), 1.71 (t, 3H)o
ED40: 1H NMR (300 MHz, CDCl3): 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)o
ED41: 1H NMR (300 MHz, CDCl3): 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)o
ED42: 1H NMR (300 MHz, CDCl3): 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)o
ED43: 1H NMR (300 MHz, CDCl3): δ 12.38 (s, 1H), 8.80 (s, 1H), 7.94-6.84 (m, 10H), 5.97 (s, 1H), 1.73 (s, 3H)o
ED44: 1H NMR (300 MHz, CDCl3): δ 12.40 (s, 1H), 7.98-6.39 (m, 12H), 5.95 (s, 1H), 1.75 (s, 3H).
The synthesis of single site Ziegler-Natta catalyst In the present invention:
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.
A solution of anhydrous MgCl2 (1.0 g) in tetrahydrofuran (THF for short, 40 mL) was stirred at 60° C. for 2 h; then to the solution was added TiCl4 (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-%.
To tetrahydrofuran (THF for short, 40 mL) was added anhydrous MgCl2 (1.0 g) and the resulting suspension was stirred for 2 hrs at 60° C. to get MgCl2 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.
To a solution of TiCl4(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 stirring. Removing the solvent under vacuum to provide Ziegler-Natta catalyst as fluid brown powders.
The following examples are the synthesis of the Ziegler-Natta catalyst according to the same procedure of example 32 (Table 1).
The following examples are synthesis of the Ziegler-Natta catalyst containing electron donor according to the same procedure of example 32 (Table 2).
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 AlEt3 (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.
The detailed experimental conditions, catalytic activity (g polymer/g catalyst), polymer molecular weight Mw (g/mol), polymer molecular weight distribution (PDI) and the polymer bulk density (g/cm3), etc. were listed in Table 3. The 13C NMR of the ethylene/1-hexene copolymer obtained in example 78 was showed in
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 AlEt3 (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.
The detailed experimental condition, catalytic activity (g polymer/g catalyst), polymer molecular weight Mw (g/mol), polymer molecular weight distribution (PDI), and the polymer bulk density (g/cm3), etc. were showed in Table 4.
| Number | Date | Country | Kind |
|---|---|---|---|
| 200610026766.2 | May 2006 | CN | national |
| PCT/CN2007/001648 | May 2007 | CN | national |
The present application is 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 from Chinese Patent Application CN 200610026766.2 filed on May 22, 2006. The subject matter and contents of the PCT International application and priority application are incorporate herein by reference.
