Method for polymerization modification of metallocene-supported polyethylene catalyst
阅读说明：本技术 一种负载茂金属聚乙烯催化剂聚合改性的方法 (Method for polymerization modification of metallocene-supported polyethylene catalyst ) 是由 贾军纪 刘明辉 王永刚 钱富娟 杨雨 郭垠 李志飞 肖爱玲 郭金彪 耿丽平 于 2021-08-02 设计创作，主要内容包括：本发明公开的是一种负载茂金属聚乙烯催化剂聚合改性的方法,在聚合评价反应装置上,氮气充分置换,缓慢搅拌下加己烷、三乙基铝和己烯-1,开始搅拌；加入酸性离子液体,所述酸性离子液体为L1-L20的一种或几种的混合,继续搅拌,加入负载茂金属聚乙烯催化剂；迅速升温,控制温度,通入乙烯反应2小时结束；过滤干燥,获得聚合改性的负载茂金属聚乙烯催化剂,进一步将负载茂金属聚乙烯催化剂称重并计算聚合活性,所述聚合活性等于聚乙烯产品重量除以催化剂重量,利用红外测定聚乙烯粉料中己烯-1的含量,改性后的负载茂金属催化剂的聚合活性及共聚能力都有所提高。(The invention discloses a method for carrying metallocene polyethylene catalyst polymerization modification, on a polymerization evaluation reaction device, fully replacing nitrogen, adding hexane, triethyl aluminum and hexene-1 under slow stirring, and starting stirring; adding acidic ionic liquid which is one or a mixture of more of L1-L20, continuing stirring, and adding a supported metallocene polyethylene catalyst; rapidly heating, controlling the temperature, and introducing ethylene to react for 2 hours; filtering and drying to obtain a polymerization modified supported metallocene polyethylene catalyst, further weighing the supported metallocene polyethylene catalyst and calculating the polymerization activity, wherein the polymerization activity is equal to the weight of a polyethylene product divided by the weight of the catalyst, and the content of hexene-1 in the polyethylene powder is measured by infrared rays, so that the polymerization activity and the copolymerization capacity of the modified supported metallocene catalyst are improved.)
1. A method for polymerization modification of a supported metallocene polyethylene catalyst is characterized by comprising the following steps:
step 1: on a 2L polymerization evaluation reaction apparatus, nitrogen was sufficiently replaced, 600mL of hexane, 1-5mL of triethylaluminum and 40mL of hexene-1 were added with slow stirring, and stirring was started;
step 2: adding 3.0mL of acidic ionic liquid which is one or a mixture of more of L1-L20, continuing stirring for 5-10 minutes, and adding 80mg of supported metallocene polyethylene catalyst;
and step 3: rapidly heating, controlling the temperature at 60-90 ℃, controlling the pressure of the reaction kettle at 0.3-2.6Mpa, and introducing ethylene to react for 2 hours;
and 4, step 4: filtering and drying to obtain a polymerization modified supported metallocene polyethylene catalyst, further weighing the supported metallocene polyethylene catalyst, calculating the polymerization activity, wherein the polymerization activity is equal to the weight of a polyethylene product divided by the weight of the catalyst, and measuring the content of hexene-1 in the polyethylene powder by utilizing infrared.
2. The method for polymerization modification of a supported metallocene polyethylene catalyst according to claim 1, wherein: the preparation method of the supported metallocene polyethylene catalyst comprises the following steps:
dividing MAO toluene solution into two equal parts, under the protection of nitrogen, cooling one part of MAO toluene solution to-10 ℃, adding metallocene compound, stirring and dissolving, and reacting for 4 hours; and adding 50g of silica gel carrier into the other part of the MAO toluene solution, starting stirring, heating to 110 ℃ for 2 hours, refluxing for 4 hours, finishing the reaction, cooling the suspension to-5 ℃, keeping the temperature, dropwise adding the first part of the MAO toluene solution in which the metallocene compound is dissolved, continuing to react for 2 hours, finishing the reaction, and stirring and draining the toluene solvent to obtain the supported metallocene catalyst.
3. The method for polymerization modification of a supported metallocene polyethylene catalyst according to claim 2, wherein: the content of the supported metallocene catalyst metal is controlled between 0.1 and 0.35 percent, and the content of MAO is controlled between 4.0 and 14.0 percent.
4. The method for polymerization modification of a supported metallocene polyethylene catalyst according to claim 1 or 2, wherein: the general formula of the metallocene is any one of a metallocene general formula 1, a metallocene general formula 2 and a metallocene general formula 3; the metallocene has the general formula 1Wherein M may be Ti or Zr or Hf; any one of R1-R5 can be H, CnH2n+1Any one of Ar and Ar;
the metallocene of the general formula 2Wherein M may be Ti or Zr or Hf; x may be CnH2nOr SiMe2(ii) a Any one of R1-R8 can be H, CnH2n+1Any one of Ar and Ar;
the metallocene of the general formula 3Wherein M can be Ti or Zr or Hf; x may be CnH2nOr SiMe2(ii) a Any one of R1-R8 can be H, CnH2n+1, Ar.
5. The method for polymerization modification of a supported metallocene polyethylene catalyst according to claim 4, wherein: the metallocene general formula 1 comprises 7 structural formulas of M1-M7, and the metallocene is prepared by the following steps
M1：M＝Zr，R1＝R2＝R3＝R4＝R5＝H；
M2：M＝Zr，R1＝CH3，R2＝R3＝R4＝R5＝H；
M3：M＝Zr，R1＝C4H9，R2＝R3＝R4＝R5＝H；
M4 is bis-indenyl zirconium dichloride;
M5：M＝Zr，R1＝C4H9，R3＝CH3，R2＝R4＝R5＝H；
M6：M＝Ti，R1＝R2＝R3＝R4＝R5＝CH3；
m7 metallocene of the general formula 1: m ═ Hf, R1＝R2＝R3＝R4＝R5＝CH3；
The metallocene general formula 2 comprises 6 structural formulas of M8-M13,
M8：M＝Ti；X＝CH2；R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝H；
M9：M＝Zr；X＝C(CH3)2；R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝H；
M10：M＝Zr；X＝C(CH3)2；R1＝R5＝Ph；R2＝R3＝R4＝R6＝R7＝R8＝H；
M11：M＝Zr；X＝Si(CH3)2；R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝H；
M12：M＝Hf；X＝C(CH3)2；R1＝R5＝Ph；R2＝R3＝R4＝R6＝R7＝R8＝H；
M13：M＝Zr；X＝Si(CH3)2；R1＝R5＝Ph；R2＝R3＝R4＝R6＝R7＝R8＝H；
the metallocene general formula 3 comprises 7 structural formulas of M14-M20,
M14：M＝Ti；X＝CH2；R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12＝H；
M15：M＝Zr；X＝CH2；R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12＝H；
M16：M＝Zr；X＝CH2；R1＝CH3；R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12＝H；
M17：M＝Ti；X＝Si(CH3)2；R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12＝H；
M18：M＝Zr；X＝Si(CH3)2；R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12＝H；
M19：M＝Zr；X＝Si(CH3)2；R1＝CH3；R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12＝H；
M20：M＝Hf；X＝Si(CH3)2；R1＝CH3；R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12＝H。
6. a process for the polymerization modification of a supported metallocene polyethylene catalyst according to claim 1, 2 or 3, characterized in that: l1 isL2 isL3 isL4 isL5 isL6 isL7 isL8 isL9 isL10 is
7. A process for the polymerization modification of a supported metallocene polyethylene catalyst according to claim 1, 2 or 3, characterized in that: l11 isL12 isL13 isL14 isL15 isL16 isL17 isL18 isL19 isL20 is
Technical Field
The invention relates to a metallocene-loaded polyethylene catalyst polymerization modification and a test method thereof, belonging to the field of polyolefin catalysts.
Background
Compared with Linear Low Density Polyethylene (LLDPE), mPE has relatively narrow molecular weight distribution and relatively uniform composition distribution, so that the film product has high strength, good longitudinal and transverse strength uniformity, good chemical extraction resistance and pollution resistance (low molecular weight polyethylene content), low film viscosity and few crystal points (low ultrahigh molecular weight polyethylene content). In addition, compared with the traditional polyethylene titanium catalyst, the metallocene polyethylene catalyst has higher copolymerization activity in copolymerization, and more copolymerizable comonomers exist, so that the application range of mPE is more extensive than that of the traditional polyethylene product.
However, the cost of the metallocene polyethylene catalyst is higher than that of the traditional catalyst due to the high price of the co-catalyst MAO, and in order to reduce the cost of the catalyst, considerable companies and research and development units try to reduce the amount of MAO on the premise of ensuring the polymerization performance of the metallocene polyethylene catalyst, and no effective and simple method for improving the activity of the metallocene polyethylene catalyst exists at present.
Disclosure of Invention
In order to solve the above-mentioned problems of the prior art, the present invention provides a metallocene catalyst having improved activity; the produced polymer branching degree is obviously improved, and the like, and the supported metallocene polyethylene catalyst is used for polymerization modification and a test method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for polymerization modification of a supported metallocene polyethylene catalyst is characterized by comprising the following steps:
a method for polymerization modification of a supported metallocene polyethylene catalyst is characterized by comprising the following steps:
step 1: on a 2L polymerization evaluation reaction apparatus, nitrogen was sufficiently replaced, 600mL of hexane, 1-5mL of triethylaluminum and 40mL of hexene-1 were added with slow stirring, and stirring was started;
step 2: adding 3.0mL of acidic ionic liquid which is one or a mixture of more of L1-L20, continuing stirring for 5-10 minutes, and adding 80mg of supported metallocene polyethylene catalyst;
and step 3: rapidly heating, controlling the temperature at 60-90 ℃, controlling the pressure of the reaction kettle at 0.3-2.6Mpa, and introducing ethylene to react for 2 hours;
and 4, step 4: filtering and drying to obtain a polymerization modified supported metallocene polyethylene catalyst, further weighing the supported metallocene polyethylene catalyst, calculating the polymerization activity, wherein the polymerization activity is equal to the weight of a polyethylene product divided by the weight of the catalyst, and measuring the content of hexene-1 in the polyethylene powder by utilizing infrared.
A method for polymerization modification of a supported metallocene polyethylene catalyst comprises the following steps:
dividing MAO toluene solution into two equal parts, under the protection of nitrogen, cooling one part of MAO toluene solution to-10 ℃, adding metallocene compound, stirring and dissolving, and reacting for 4 hours; and adding 50g of silica gel carrier into the other part of the MAO toluene solution, starting stirring, heating to 110 ℃ for 2 hours, refluxing for 4 hours, finishing the reaction, cooling the suspension to-5 ℃, keeping the temperature, dropwise adding the first part of the MAO toluene solution in which the metallocene compound is dissolved, continuing to react for 2 hours, finishing the reaction, and stirring and draining the toluene solvent to obtain the supported metallocene catalyst. The amount of MAO in toluene was chosen as desired.
Preferably, the supported metallocene catalyst metal content is controlled between 0.1-0.35%, and the MAO content is controlled between 4.0-14.0%.
Preferably, the metallocene compound has any one of a general formula 1, a general formula 2, and a general formula 3; the metallocene has the general formula 1Wherein M may be Ti or Zr or Hf; any one of R1-R5 can be H, CnH2n+1Any one of Ar and Ar;
the metallocene of the general formula 2Wherein M may be Ti or Zr or Hf; x may be CnH2nOr SiMe2(ii) a Any one of R1-R8 can be H, CnH2n+1Any one of Ar and Ar;
the metallocene of the general formula 3Wherein M can be Ti or Zr or Hf; x may be CnH2nOr SiMe2(ii) a Any one of R1-R8 can be H, CnH2n+1, Ar.
Preferably, said metallocene of formula 1 comprises 7 structural formulae M1-M7, said M1: m ═ Zr; r1＝R2＝R3＝R4＝R5＝H；
M2：M＝Zr；R1＝CH3；R2＝R3＝R4＝R5＝H；M3：M＝Zr；R1＝C4H9；R2＝R3＝R4＝R5H; m4 is bis-indenyl zirconium dichloride; m5: m ═ Zr; r1＝C4H9；R3＝CH3；R2＝R4＝R5＝H；
M6：M＝Ti；R1＝R2＝R3＝R4＝R5＝CH3(ii) a M7 metallocene of the general formula 1: m ═ Hf; r1＝R2＝R3＝R4＝R5＝CH3(ii) a The metallocene of the general formula 2 comprises 6 structural formulas M8-M13, M8: m is Ti; x ═ CH2；
R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝H；M9：M＝Zr；X＝C(CH3)2；
R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝H；M10：M＝Zr；X＝C(CH3)2；
R1＝R5＝Ph；R2＝R3＝R4＝R6＝R7＝R8＝H；M11：M＝Zr；X＝Si(CH3)2；
R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝H；M12：M＝Hf；X＝C(CH3)2；
R1＝R5＝Ph；R2＝R3＝R4＝R6＝R7＝R8＝H；M13：M＝Zr；X＝Si(CH3)2；
R1＝R5＝Ph；R2＝R3＝R4＝R6＝R7＝R8＝H；
The metallocene of the general formula 3 comprises 7 structural formulas M14-M20, M14: m is Ti; x ═ CH2；
R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12＝H；
M15：M＝Zr；X＝CH2；
R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12H; m16 metallocene of the general formula 3: m ═ Zr; x ═ CH2；
R1＝CH3；R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12H; m17 metallocene of the general formula 3: m is Ti;
X＝Si(CH3)2；
R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12＝H；
M18：M＝Zr；X＝Si(CH3)2；
R1＝R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12＝H；
M19：M＝Zr；X＝Si(CH3)2；
R1＝CH3；R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12＝H；
M20：M＝Hf；X＝Si(CH3)2；
R1＝CH3；R2＝R3＝R4＝R5＝R6＝R7＝R8＝R9＝R10＝R11＝R12＝H。
preferably, L1 isL2 isL3 isL4 isL5 isL6 isL7 isL8 isL9 isL10 isL11 isL12 isL13 isL14 isL15 isL16 is L18 isL19 isL20 is
A method for testing a supported metallocene polyethylene catalyst comprises the following steps:
fully replacing nitrogen in a 2L polymerization evaluation reaction device, adding 3mL of any one of 600mL of hexane, 2mL-5mL of triethylaluminum and L1-L20 under slow stirring, stirring for 5 minutes, adding 80mg of a self-made supported metallocene polyethylene catalyst taking any one of M1-M20 as a main catalyst, rapidly heating to 70-100 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 10-20Kg in a reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, and measuring the content of hexene-1 in polyethylene powder by utilizing infrared to obtain parameters.
Has the advantages that: the method can obviously improve the polymerization activity and the copolymerization capability of the supported metallocene catalyst, has simple process means and saves the cost.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to the following examples.
Dividing the MAO toluene solution into two equal parts, under the protection of nitrogen, cooling one part of MAO toluene solution to-10 ℃, adding a metallocene compound, stirring and dissolving, and reacting for 4 hours; and adding 50g of silica gel carrier into the other part of the MAO toluene solution, starting stirring, carrying out programmed heating, heating to 110 ℃ for 2 hours, refluxing for 4 hours, finishing the reaction, cooling the suspension to-5 ℃, keeping the temperature, dropwise adding the first part of the MAO toluene solution in which the metallocene compound is dissolved, continuing to react for 2 hours after dropwise adding, finishing the reaction, and keeping stirring and draining the toluene solvent to obtain the supported metallocene catalyst.
The content of the self-made load metallocene catalyst is controlled between 0.10 and 0.35 percent, and the content of Al is controlled between 4.0 and 14.0 percent. The preparation conditions of the supported metallocene catalyst and the content of active components of the catalyst are as follows:
example 1 and comparative example 1:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 2mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L1 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M20 as a main catalyst, rapidly heating to 70 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 10Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 1 no ionic liquid was added and the rest of the procedure was exactly the same. The polymerization activity and the polymer branching degree data of the catalyst are shown in the attached table and the same below.
Example 2 and comparative example 2:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 3mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L2 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M19 as a main catalyst, rapidly heating to 80 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 10Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 2 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 3 and comparative example 3:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 4mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L3 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M18 as a main catalyst, rapidly heating to 90 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 10Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 3 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 4 and comparative example 4:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 4mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L4 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M17 as a main catalyst, rapidly heating to 100 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 10Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 4 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 5 and comparative example 5:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 2mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L5 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M16 as a main catalyst, rapidly heating to 70 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 10Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 5 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 6 and comparative example 6:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 3mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L6 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M15 as a main catalyst, rapidly heating to 80 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 10Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 6 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 7 and comparative example 7:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 4mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L7 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M14 as a main catalyst, rapidly heating to 80 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 15Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 7 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 8 and comparative example 8:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 5mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L8 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M13 as a main catalyst, rapidly heating to 100 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 15Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 8 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 9 and comparative example 9:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 2mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L9 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M12 as a main catalyst, rapidly heating to 70 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 15Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 9 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 10 and comparative example 10:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 3mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L0 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M11 as a main catalyst, rapidly heating to 80 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 15Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 10 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 11 and comparative example 11:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 4mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L11 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M10 as a main catalyst, rapidly heating to 90 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 15Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 11 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 12 and comparative example 12:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 5mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L12 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M9 as a main catalyst, rapidly heating to 100 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 15Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 12 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 13 and comparative example 13:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 2mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L13 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M8 as a main catalyst, rapidly heating to 70 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 15Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 13 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 14 and comparative example 14:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 3mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L14 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M7 as a main catalyst, rapidly heating to 70 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 20Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 14 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 15 and comparative example 15:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 4mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L15 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M6 as a main catalyst, rapidly heating to 90 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 20Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 15 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 16 and comparative example 16:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 5mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L16 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M5 as a main catalyst, rapidly heating to 100 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 20Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 16 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 17 and comparative example 17:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 2mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L17 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M4 as a main catalyst, rapidly heating to 70 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 20Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 17 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 18 and comparative example 18:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 3mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L18 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M3 as a main catalyst, rapidly heating to 80 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 20Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 18 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 19 and comparative example 19:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 4mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L19 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M2 as a main catalyst, rapidly heating to 90 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 20Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 19 no ionic liquid was added and the rest of the procedure was exactly the same.
Example 20 and comparative example 20:
replacing 2L of a polymerization kettle with nitrogen for more than three times, adding 600mL of hexane, 5mL of triethylaluminum (1mol/L of solvent is hexane) and 3mL of L20 ionic liquid at room temperature, stirring for 5 minutes, adding 80mg of a self-prepared supported metallocene polyethylene catalyst (see a preparation table of the supported metallocene catalyst) taking M1 as a main catalyst, rapidly heating to 100 ℃, adding 40mL of hexene-1, introducing ethylene gas, keeping 20Kg in the reaction kettle, reacting for 2 hours, stopping the reaction, taking out polyethylene, drying, weighing to calculate polymerization activity, and measuring the branching degree. Comparative example 20 no ionic liquid was added and the rest of the procedure was exactly the same.
Table 1: the general formula of the metallocene compound
Table 2: metallocene Compound numbering
Table 3: ionic liquid numbering
TABLE 3 examples and comparative examples test data
From the polymerization result, the polymerization activity and the copolymerization capability of the modified supported metallocene catalyst are obviously improved.
Finally, it should be noted that the present invention is not limited to the above embodiments, and many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.