CN113817084A - Polypropylene catalyst modification and test method thereof - Google Patents
Polypropylene catalyst modification and test method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F210/06—Propene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/655—Pretreating with metals or metal-containing compounds with aluminium or compounds thereof
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/657—Pretreating with metals or metal-containing compounds with metals or metal-containing compounds, not provided for in groups C08F4/653 - C08F4/656
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a polypropylene catalyst modification and test method, wherein 5-50g of polypropylene catalyst, 20-90g of 68# white oil and 20-60g of pharmaceutical-grade white vaseline are added into a three-neck flask with a well replaced nitrogen gas, after stirring for 10 minutes, the temperature is controlled to be 0-25 ℃, 0.1-10g of ionic liquid of any one of L1-L20 is added, and stirring is carried out for 5-300min, so as to obtain a modified polypropylene catalyst system; particularly, from the results of homopolymerization and impact copolymerization of the catalyst, the activity of the catalyst is improved and the copolymerization performance is improved after the catalyst is modified by the ionic liquid.
Description
Technical Field
The invention relates to catalyst modification, a test and a test method thereof, in particular to polypropylene catalyst modification and a test method thereof, belonging to the field of polyolefin catalysts.
Background
Polypropylene is an important variety in five general synthetic resins, has the characteristics of no toxicity, no odor, low density, good rigidity, high impact strength, chemical corrosion resistance and the like, can be used for manufacturing woven products, injection-molded products, films, pipes and the like, and is widely applied to the fields of packaging, automobiles, household appliances, building materials, daily necessities and the like. The polypropylene industry in our country will remain a fast growth in the coming years.
Catalyst technology is central to polypropylene technology. Ziegler-Natta catalysts still occupy the absolute mainstream. The research on how to improve the performance of the Ziegler-Natta polypropylene catalyst, match and adapt to a polypropylene production device and develop high-performance products is always a hot topic for the development of new polypropylene products.
The external electron donor plays an important role in a polypropylene catalytic system and influences the directional polymerization capability and the hydrogen regulation sensitivity of the catalytic system. A composite external electron donor technology is developed, two or more external electron donors are added in a polymerization reaction at the same time, wherein one external electron donor is generally dicyclopentyldimethoxysilane, and another external electron donor which has high hydrogen regulation sensitivity and low orientation capability is selected, so that a polypropylene product with high melt index, high isotacticity and relatively wide molecular weight distribution is obtained. For example, the exxon chemical company adopts dicyclopentyl dimethoxy silane/propyl triethoxy silane to compound an external electron donor, obtains a polypropylene product with high melt index and medium molecular weight distribution, and has the advantages of impact resistance, high flexural modulus and good processability. The company also adopts dicyclopentyl dimethoxy silane/tetraethoxysilane composite external electron donor to obtain polypropylene products with high melt index and medium molecular weight distribution.
Dow company develops advanced electron donor technology (ADT) suitable for Unipol gas-phase polypropylene process, siloxane/monoester composite external electron donor is adopted, monoester external electron donor is different from siloxane, polymerization activity is reduced when reaction temperature is increased, and a catalytic system of the composite external electron donor has the characteristic of self-quenching, so that the operation stability of a gas-phase fluidized bed is greatly improved, and the risk of implosion caused by local hot spots is reduced. At present, the performance of polypropylene products is improved by improving the matching capability of external electron donors and polypropylene catalysts in a common way. At present, a simple and efficient method for modifying a polypropylene catalytic system is lacked.
Disclosure of Invention
In order to solve the above-mentioned problems of the prior art, the present invention provides a modification method of a polypropylene catalyst and a test method thereof, which have the technical characteristics of improving the polymerization activity of the polypropylene catalyst, improving the copolymerization performance of the catalyst, and the like.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for modifying a polypropylene catalyst, which comprises the following steps:
adding 5-50g of polypropylene catalyst, 20-90g of 68# white oil and 10-60g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 0-25 ℃, adding 0.1-10g of any one of ionic liquid L1-L20, and stirring for 5-300 minutes to obtain a modified polypropylene catalyst system.
A method for modifying a polypropylene catalyst is characterized by comprising the following steps:
adding 5-50g of polypropylene catalyst and 20-90g of 68# white oil into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 0-30 ℃, adding 0.1-10g of any one of ionic liquid L1-L20, and stirring for 5-300 minutes to obtain a modified polypropylene catalyst system.
A method for modifying a modified polypropylene catalyst comprises the following steps: l1 is
L2 is
L3 is
L4 is
L5 is
L6 is
L7 is
L8 is
L9 is
L10 is
L11 is
L12 is
L13 is
L14 is
L15 is
L16 is
L17 is
L18 is
L19 is
L20 is.
A test method of a modified polypropylene catalyst comprises the following steps:
propylene homopolymerization:
replacing 5L of polymerization mould device by nitrogen, replacing propylene for the last time, then adding 2.0Kg of propylene, 4mL of hexane solution of triethyl aluminum, 200mg of modified catalyst system and 2mL of cyclohexyl methyl dimethoxy silane in three times, quickly heating, controlling the reaction temperature to be 70 ℃, reacting for 2 hours, stopping the reaction, drying polypropylene, weighing, calculating polymerization activity and measuring isotacticity;
impact copolymerization:
a 5L double-kettle series polymerization model device is replaced by nitrogen, propylene is replaced for the last time, 2.0Kg of propylene, 4mL of hexane solution of triethyl aluminum, 200mg of modified catalyst system and 2mL of cyclohexyl methyl dimethoxy silane are added into the first reaction kettle in three times, the temperature is quickly raised, the reaction temperature is controlled to be 70 ℃, the reaction is carried out for 1 hour, and the reaction is stopped. Keeping the second kettle at normal pressure, pressing all polypropylene homopolymerized particles into the second polymerization kettle by utilizing the residual pressure of propylene, starting stirring, preparing ethylene: adding 1:4 (mass ratio) of propylene into a second polymerization reactor, controlling the reaction pressure to be 10Kg, reacting at the reaction temperature of 80 ℃ for 1 hour, and stopping the reaction. And drying the polypropylene, weighing, calculating polymerization activity and measuring the content of the ethylene-propylene copolymer.
Has the advantages that: the polymerization activity of the polypropylene catalyst can be improved, and the copolymerization performance of the catalyst can be improved; particularly, from the results of homopolymerization and impact copolymerization of the catalyst, the activity of the catalyst is improved and the copolymerization performance is improved after the catalyst is modified by the ionic liquid.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Drying and weighing the polymerization product to obtain polymerization activity (polymerization activity ═ product weight ÷ catalyst weight); the molecular weight distribution of the polymer was characterized by the melt index of the product by measuring the weight at 2.16Kg and 10Kg to give a melt ratio value of melt index (10Kg) ÷ melt index (2.16 Kg).
Example 1
10g of polypropylene catalyst and 90g of 68# white oil are added into a three-neck flask which is well replaced by nitrogen, stirred for 10 minutes, then the temperature is controlled at 0 ℃, 0.1g of L1 ionic liquid is added, and stirred for 5 minutes, thus obtaining the modified polypropylene catalyst system.
Example 2
Adding 10g of polypropylene catalyst, 70g of 68# white oil and 20g of pharmaceutical-grade white vaseline into a three-neck flask replaced by nitrogen, stirring for 10 minutes, controlling the temperature to be 5 ℃, adding 1.0mL of L2 ionic liquid, and stirring for 50 minutes to obtain a modified polypropylene catalyst system.
Example 3
Adding 10g of polypropylene catalyst, 50g of 68# white oil and 40g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 10 ℃, adding 1.5g of L3 ionic liquid, and stirring for 100 minutes to obtain a modified polypropylene catalyst system.
Example 4
Adding 10g of polypropylene catalyst, 30g of 68# white oil and 60g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 15 ℃, adding 2.0g of L4 ionic liquid, and stirring for 200 minutes to obtain a modified polypropylene catalyst system.
Example 5
20g of polypropylene catalyst and 80g of 68# white oil are added into a three-neck flask which is well replaced by nitrogen, stirred for 10 minutes, then the temperature is controlled to be 20 ℃, 2.5g of L5 ionic liquid is added, and stirred for 300 minutes, so that a modified polypropylene catalyst system is obtained.
Example 6
30g of polypropylene catalyst and 70g of 68# white oil are added into a three-neck flask with replaced nitrogen, stirred for 10 minutes, then the temperature is controlled at 25 ℃, 0.5g of L6 ionic liquid is added, and the mixture is stirred for 100 minutes, so that a modified polypropylene catalyst system is obtained.
Example 7
Adding 30g of polypropylene catalyst, 55g of 68# white oil and 15g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 20 ℃, adding 1.0g of L7 ionic liquid, and stirring for 30 minutes to obtain a modified polypropylene catalyst system.
Example 8
Adding 30g of polypropylene catalyst, 30g of 68# white oil and 40g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 5 ℃, adding 1.5g of L8 ionic liquid, and stirring for 60 minutes to obtain a modified polypropylene catalyst system.
Example 9
Adding 5g of polypropylene catalyst, 50g of 68# white oil and 45g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 15 ℃, adding 3.0g of L9 ionic liquid, and stirring for 100 minutes to obtain a modified polypropylene catalyst system.
Example 10
Adding 50g of polypropylene catalyst, 25g of 68# white oil and 25g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 20 ℃, adding 3.0g of L10 ionic liquid, and stirring for 150 minutes to obtain a modified polypropylene catalyst system.
Example 11
Adding 10g of polypropylene catalyst, 80g of 68# white oil and 10g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 0 ℃, adding 0.5g of L11 ionic liquid, and stirring for 30 minutes to obtain a modified polypropylene catalyst system.
Example 12
Adding 10g of polypropylene catalyst, 70g of 68# white oil and 20g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 15 ℃, adding 2.0g of L12 ionic liquid, and stirring for 50 minutes to obtain a modified polypropylene catalyst system.
Example 13
Adding 10g of polypropylene catalyst, 50g of 68# white oil and 40g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 5 ℃, adding 1.5g of L13 ionic liquid, and stirring for 100 minutes to obtain a modified polypropylene catalyst system.
Example 14
Adding 10g of polypropylene catalyst, 60g of 68# white oil and 30g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 25 ℃, adding 2.0g of L14 ionic liquid, and stirring for 200 minutes to obtain a modified polypropylene catalyst system.
Example 15
Adding 20g of polypropylene catalyst, 70g of 68# white oil and 10g of pharmaceutical-grade white vaseline into a three-neck flask replaced by nitrogen, stirring for 10 minutes, controlling the temperature to be 5 ℃, adding 2.5g of L-ionic liquid, and stirring for 300 minutes to obtain a modified polypropylene catalyst system.
Example 16
Adding 30g of polypropylene catalyst, 50g of 68# white oil and 20g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 15 ℃, adding 0.5g of L16 ionic liquid, and stirring for 100 minutes to obtain a modified polypropylene catalyst system.
Example 17
Adding 30g of polypropylene catalyst, 40g of 68# white oil and 30g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 25 ℃, adding 1.0g of L17 ionic liquid, and stirring for 30 minutes to obtain a modified polypropylene catalyst system.
Example 18
Adding 30g of polypropylene catalyst, 30g of 68# white oil and 40g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 5 ℃, adding 1.5g of L18 ionic liquid, and stirring for 60 minutes to obtain a modified polypropylene catalyst system.
Example 19
Adding 5g of polypropylene catalyst, 60g of 68# white oil and 35g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 15 ℃, adding 3.0g of L19 ionic liquid, and stirring for 100 minutes to obtain a modified polypropylene catalyst system.
Example 20
Adding 50g of polypropylene catalyst, 30g of 68# white oil and 20g of pharmaceutical-grade white vaseline into a three-neck flask with replaced nitrogen, stirring for 10 minutes, controlling the temperature to be 20 ℃, adding 3.0g of L20 ionic liquid, and stirring for 150 minutes to obtain a modified polypropylene catalyst system.
Attached table 1: ionic liquid numbering
Comparative examples 1 to 20: the procedure was exactly the same as in examples 1 to 20 except that the ionic liquid was removed, to obtain an unmodified polypropylene catalyst for evaluation and comparison of polymerization.
Polymerization evaluation operation and results:
propylene homopolymerization:
the final propylene replacement was carried out in three times using a 5L polymerization model apparatus replaced with nitrogen, 2.0Kg of propylene, 4mL of a triethylaluminum hexane solution, 20mg of a catalyst system solid content and 2mL of cyclohexylmethyldimethoxysilane, the temperature was rapidly raised and controlled at 70 ℃ for 2 hours, and the reaction was stopped. The polypropylene is dried, weighed, the polymerization activity is calculated and the isotacticity is determined.
TABLE 2 accompanying test results of examples 1-10 and comparative examples 1-10
| Serial number | Polymerization Activity (gPP/gcat) | Polymerization Activity (gPP/gcat) | Degree of isotacticity (%) | Degree of isotacticity (%) |
| 1 | 29020 | 31000 | 95.3 | 95.3 |
| 2 | 29004 | 29481 | 95.3 | 95.9 |
| 3 | 29400 | 31024 | 95.1 | 96.7 |
| 4 | 29006 | 32188 | 95.3 | 97.0 |
| 5 | 28314 | 32456 | 95.3 | 97.1 |
| 6 | 29157 | 30038 | 95.3 | 95.9 |
| 7 | 29411 | 30859 | 95.3 | 96.0 |
| 8 | 29333 | 31004 | 95.3 | 96.0 |
| 9 | 28991 | 29401 | 95.3 | 97.0 |
| 10 | 29559 | 31236 | 95.3 | 97.3 |
Note: polymerization activity and isotacticity data in the left column are comparative example catalyst data; data for the examples in the right column.
Impact copolymerization:
a 5L double-kettle series polymerization model device is replaced by nitrogen, propylene is replaced for the last time, 2.0Kg of propylene, 4mL of hexane solution of triethyl aluminum, 20mg of solid content of a catalyst system and 2mL of cyclohexyl methyl dimethoxy silane are added into the first reaction kettle in three times, the temperature is rapidly increased, the reaction temperature is controlled to be 70 ℃, the reaction is carried out for 1 hour, and the reaction is stopped. Keeping the second kettle at normal pressure, pressing all polypropylene homopolymerized particles into the second polymerization kettle by utilizing the residual pressure of propylene, starting stirring, preparing ethylene: adding 1:4 (mass ratio) of propylene into a second polymerization reactor, controlling the reaction pressure to be 10Kg, reacting at the reaction temperature of 80 ℃ for 1 hour, and stopping the reaction. And drying the polypropylene, weighing, calculating polymerization activity and measuring the content of the ethylene-propylene copolymer.
TABLE 3 accompanying test results of examples 11 to 20 and comparative examples 11 to 20
| Serial number | Polymerization Activity (gPP/gcat) | Polymerization Activity (gPP/gcat) | Rubber phase content (%) | Rubber phase content (%) |
| 1 | 26333 | 26412 | 5.44 | 5.66 |
| 2 | 26142 | 27108 | 5.44 | 7.01 |
| 3 | 25944 | 26911 | 5.44 | 6.88 |
| 4 | 26037 | 26019 | 5.44 | 7.30 |
| 5 | 26412 | 26933 | 5.44 | 6.44 |
| 6 | 26039 | 26359 | 5.44 | 5.49 |
| 7 | 26111 | 17211 | 5.44 | 5.61 |
| 8 | 25987 | 26906 | 5.44 | 5.93 |
| 9 | 24036 | 25403 | 5.44 | 6.42 |
| 10 | 26138 | 27222 | 5.44 | 6.79 |
Note: polymerization activity and isotacticity data in the left column are comparative example catalyst data; data for the examples in the right column.
The content of the rubber phase is the total amount ratio, and the test method comprises the following steps: weighing 1g of impact-resistant polypropylene, leaching the impact-resistant polypropylene with xylene, wherein the rest solid is homopolymerized polypropylene, and the leached and dissolved impact-resistant polypropylene is a rubber phase.
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.
Claims (5)
1. A method for modifying a polypropylene catalyst is characterized by comprising the following steps:
step 1: adding 5-50g of polypropylene catalyst, 20-90g of 68# white oil and 10-60g of pharmaceutical white vaseline into a three-neck flask with replaced nitrogen;
step 2: stirring for 10 min, controlling the temperature at 0-25 ℃, adding 0.1-10g of one or more of L1-L20 ionic liquids, and stirring for 5-300min to obtain the modified polypropylene catalyst system.
2. A method for modifying a polypropylene catalyst is characterized by comprising the following steps:
step 1: adding 5-50g of polypropylene catalyst and 20-90g of 68# white oil into a three-neck flask with replaced nitrogen;
step 2: stirring for 10 min, controlling the temperature to be 0-30 ℃, adding 0.1-10g of any one of the ionic liquids L1-L20, and stirring for 5-300min to obtain the modified polypropylene catalyst system.
3. The method for modifying a modified polypropylene catalyst according to claim 1 or 2, wherein: l1 is
L2 is
L3 is
L4 is
L5 is
L6 is
L7 is
L8 is
L9 is
L10 is
4. The method for modifying a modified polypropylene catalyst according to claim 1 or 2, wherein:
l11 is
L12 is
L13 is
L14 is
L15 is
L16 is
L17 is
L18 is
L19 is
L20 is.
5. A test method of a modified polypropylene catalyst is characterized by comprising the following steps:
propylene homopolymerization:
replacing 5L of polymerization mould device by nitrogen, replacing propylene for the last time, then adding 2.0Kg of propylene, 4mL of hexane solution of triethyl aluminum, 200mg of modified catalyst system and 2mL of cyclohexyl methyl dimethoxy silane in three times, quickly heating, controlling the reaction temperature to be 70 ℃, reacting for 2 hours, stopping the reaction, drying polypropylene, weighing, calculating polymerization activity and measuring isotacticity;
impact copolymerization:
replacing 5L of double-kettle series polymerization mould test device by nitrogen, replacing propylene for the last time, adding 2.0Kg of propylene, 4mL of hexane solution of triethyl aluminum, 200mg of modified catalyst system and 2mL of cyclohexyl methyl dimethoxy silane into a first reaction kettle in three times, quickly heating, controlling the reaction temperature to be 70 ℃, reacting for 1 hour, stopping the reaction, keeping the second kettle at normal pressure, completely pressing polypropylene homopolymerized particles into a second polymerization kettle by utilizing the residual pressure of propylene, starting stirring, and preparing ethylene: adding propylene in a mass ratio of 1:4 into a second polymerization reactor, controlling the reaction pressure to be 10Kg, reacting at the reaction temperature of 80 ℃ for 1 hour, stopping the reaction, drying the polypropylene, weighing, calculating the polymerization activity and measuring the content of the ethylene-propylene copolymer.
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