CN112745355A - Complex for preparing highly branched poly (4-methyl-1-pentene) material and preparation method thereof - Google Patents
Complex for preparing highly branched poly (4-methyl-1-pentene) material and preparation method thereof Download PDFInfo
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- CN112745355A CN112745355A CN202110043672.0A CN202110043672A CN112745355A CN 112745355 A CN112745355 A CN 112745355A CN 202110043672 A CN202110043672 A CN 202110043672A CN 112745355 A CN112745355 A CN 112745355A
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- 229920000306 polymethylpentene Polymers 0.000 title abstract description 19
- 239000011116 polymethylpentene Substances 0.000 title abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 title abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 53
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000071 diazene Inorganic materials 0.000 claims abstract description 34
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 25
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 8
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 7
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- WFGHUOGOUOTVBO-UHFFFAOYSA-N 2,6-dipropylaniline Chemical compound CCCC1=CC=CC(CCC)=C1N WFGHUOGOUOTVBO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000012968 metallocene catalyst Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- YMAZWFQPRHQWTA-UHFFFAOYSA-N 4-methoxy-2,6-dipropylaniline Chemical compound CCCC1=CC(OC)=CC(CCC)=C1N YMAZWFQPRHQWTA-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a complex for preparing a highly branched poly (4-methyl-1-pentene) material and a preparation method thereof; when the diimine palladium complex is applied to 4-methyl-1-pentene polymerization, the reaction conditions are mild, and the polymerization reaction does not need to be carried out under the harsh anhydrous and anaerobic conditions; and (2) introducing propyl at the ortho-position of the aromatic ring of the imine nitrogen atom, wherein the propyl can provide dynamic steric hindrance for the complex in the catalytic polymerization process due to the introduction of the propyl, so that the spatial environment of the Pd catalytic active center is finely adjusted, the branching degree and the molecular weight of the polymer are regulated, and the highly branched poly (4-methyl-1-pentene) is obtained.
Description
Technical Field
The invention belongs to the field of polyolefin preparation, and particularly relates to a complex for preparing a highly branched poly (4-methyl-1-pentene) material and a preparation method thereof.
Background
The poly-4-methyl-1-pentene may be formed by injection molding, blow molding, extrusion molding, etc. The method is mainly used for manufacturing medical appliances (such as syringes), physical and chemical experimental appliances, special feeders for electronic cookers, baking plates, release paper, heat-resistant wire coatings and the like. The monomer 4-methyl-1-pentene is prepared by propylene dimerization, and then the polymerization is carried out by a catalyst.
In recent years, the research using 4-methyl-1-pentene as a homo-or comonomer has focused mainly on metallocene catalysts and non-metallocene catalysts of the early transition metal system. However, the metallocene catalyst or non-metallocene catalyst of the early transition metal system has high manufacturing cost, and the defects that the cocatalyst Methyl Aluminoxane (MAO) is expensive and has large dosage, the active center is easily deactivated by the action of polar functional groups, the copolymerization of olefin and polar monomer cannot be catalyzed, the shape and the particle size of the polymer are difficult to control, and the like, generally exist. The research on the preparation of the highly branched poly-4-methyl-1-pentene material by the nickel palladium diimine catalyst is less, and the invention provides the complex for preparing the highly branched poly-4-methyl-1-pentene material and the preparation method thereof.
Disclosure of Invention
The invention aims to provide a diimine palladium complex with propyl substituted ortho-position.
Another object of the present invention is to provide a process for producing the above diimine palladium complex.
Still another object of the present invention is to provide the use of the above diimine palladium complex in the polymerization of 4-methyl-1-pentene.
The above purpose of the invention is realized by the following technical scheme:
a diimine palladium complex having the formula (I):
when the diimine palladium complex catalyst is applied to 4-methyl-1-pentene polymerization, the reaction conditions are mild, and the polymerization reaction does not need to be carried out under the harsh anhydrous and anaerobic conditions. And (2) introducing propyl at the ortho-position of the aromatic ring of the imine nitrogen atom, wherein the propyl can provide dynamic steric hindrance for the complex in the catalytic polymerization process due to the introduction of the propyl, so that the spatial environment of the Pd catalytic active center is finely adjusted, the branching degree and the molecular weight of the polymer are regulated, and the highly branched poly (4-methyl-1-pentene) is obtained.
A preparation method of a diimine palladium complex comprises the following steps:
1. under the nitrogen atmosphere, trimethylaluminum is firstly used for activating 2, 6-dipropylaniline, and then the trimethylaluminum and acenaphthenequinone are subjected to a ketone-amine condensation reaction to generate a diimine ligand.
Wherein the molar ratio of the 2, 6-dipropylaniline to the trimethylaluminum to the acenaphthenequinone is 1:1: 2.4.
Wherein the solvent used in the reaction is toluene.
2. Under the conditions of nitrogen atmosphere and room temperature, dissolving diimine ligand and (COD) PdMeCl in an organic solvent, and stirring for reaction for a period of time to obtain diimine palladium complex.
Wherein the molar ratio of the diimine ligand to the (COD) PdMeCl is 1: 1.2.
Wherein the organic solvent is dichloromethane.
Wherein the reaction time is 8-12 hours.
The synthesis reaction formula is as follows:
the invention also provides the application of the diimine palladium complex serving as a catalyst in 4-methyl-1-pentene polymerization.
The diimine palladium complex serving as a 4-methyl-1-pentene polymerization catalyst can be used for preparing poly (4-methyl-1-pentene) under the conditions that the polymerization time is 4 hours, the polymerization temperature is 30 ℃ and the polymerization pressure is 0.2-20 atm.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the ortho position of the aromatic ring of the imine nitrogen atom is introduced with propyl, so that the propyl provides dynamic steric hindrance in the catalytic polymerization process, the spatial environment of the Pd catalytic active center is further finely adjusted, and the branching degree and the molecular weight of the polymer are regulated and controlled; highly branched poly-4-methyl-1-pentene is obtained.
Drawings
FIG. 1 is a single crystal structural diagram of a diimine palladium complex prepared in example 8 of this invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
In the following examples, the number average molecular weight of the poly (4-methyl-1-pentene) produced was measured by gel permeation chromatography.
Example 1
This example provides a diimine ligand, which is synthesized as follows.
Under the conditions of nitrogen atmosphere and room temperature, 20mL of toluene and 2, 6-dipropyl-4-methoxyaniline (12mmol) are added into a 100mL branched bottle, and then 12mL of trimethylaluminum (1.0M, 12mmol) are added; raising the reaction temperature to 110 ℃, cooling the reaction temperature to room temperature after reacting for 2 hours, and then adding acenaphthenequinone (5 mmol); at the moment, the reaction system changes from colorless to deep red and emits a large amount of heat; continuing to react for 6 hours at 110 ℃, then cooling to 0 ℃, and stopping the reaction system by using 5% sodium hydroxide ice water solution; the organic phase was extracted with ethyl acetate and then with anhydrous MgSO4Drying, and spin-drying the solvent under reduced pressure to obtain an orange oil; the product was isolated by silica gel column eluting with a eluent (petroleum ether: ethyl acetate 15: 1); recrystallization from ethanol gave pale yellow crystals with a yield of 68.9%.
Example 2
This example provides a diimine palladium complex, which is synthesized as follows.
Under nitrogen protection, 20mL of diimine ligand (0.5mmol), (COD) PdMeCl (0.6mmol) and dichloromethane were added to a Schlenk flask with a mouth, stirred at room temperature for 12 hours, and then the solvent was evaporated at room temperature under reduced pressure to about 5mL, and 20mL of n-hexane was added, at which time a large amount of precipitate was generated. Filtration through a G4 filter bulb and washing of the precipitate with 3X 10mL of n-hexane followed by vacuum drying gave the diimine palladium complex as a yellow solid in 78.6% yield.
Example 3
This example provides a highly branched poly (4-methyl-1-pentene) which is prepared as follows.
The glassware and the stirring magnetrons used were dried in an oven (120 ℃ C.) and all polymerization experiments were carried out in the absence of water and oxygen. 250mL of the mixture is continuously vacuumizedBaking the round-bottomed flask with the branch mouth for more than 1h under an infrared lamp at the temperature of 150 ℃ to remove moisture and air completely; introducing nitrogen for replacement twice, and introducing nitrogen to normal pressure; the water bath was kept constant at 30 ℃ and a metered amount of chlorobenzene was added, dissolved with stirring and injected with 2M of the monomer and 10. mu. mol of diimine palladium complex in 2mL of dichloromethane. After 4h of polymerization the reaction was stopped and Et was used3Precipitating in methanol after SiH is terminated, dissolving the precipitated polymer in petroleum ether, separating with silica gel column, concentrating, precipitating in methanol, washing the obtained polymer with ethanol for three times, and vacuum drying to constant weight. 3.15g of poly (4-methyl-1-pentene) with a number-average molecular weight of 12985g mol-1The molecular weight distribution was 1.97 and the degree of branching was 397 branches/1000C.
Example 4
This example provides poly (4-methyl-1-pentene) which is prepared as follows.
The same polymerization conditions as in example 3 were used, and the reaction pressure was 5atm instead of 0.2 atm. 3.76g of poly (4-methyl-1-pentene) with a number-average molecular weight of 16379g mol-1The molecular weight distribution was 1.82 and the degree of branching was 367 branches/1000C.
Example 5
This example provides poly (4-methyl-1-pentene) which is prepared as follows.
The same polymerization conditions as in example 3 were used, and the reaction pressure was 10atm instead of 0.2 atm. 4.02g of poly (4-methyl-1-pentene) was obtained, having a number-average molecular weight of 18354g mol-1The molecular weight distribution was 1.78 and the degree of branching was 330 branches/1000C.
Example 6
This example provides poly (4-methyl-1-pentene) which is prepared as follows.
The same polymerization conditions as in example 3 were used, and the reaction pressure was 15atm instead of 0.2 atm. To obtain 4.43g of poly (4-methyl-1-pentene) having a number average molecular weight of 15631g mol-1The molecular weight distribution was 1.73 and the degree of branching was 316 branches/1000C.
Example 7
This example provides poly (4-methyl-1-pentene) which is prepared as follows.
And example 3 phaseThe same polymerization conditions, the reaction pressure is 20atm instead of 0.2 atm. To obtain 4.86g of poly (4-methyl-1-pentene) having a number average molecular weight of 16235g mol-1The molecular weight distribution was 1.67 and the degree of branching was 297 branches/1000C.
From examples 3 to 7, the diimine palladium complex prepared by the invention has a good effect when used for preparing a highly branched poly (4-methyl-1-pentene) material. However, the research using 4-methyl-1-pentene as a homo-or comonomer mainly focuses on the metallocene catalyst and the non-metallocene catalyst of the pre-transition metal system, but the metallocene catalyst or the non-metallocene catalyst of the pre-transition metal system has high manufacturing cost, and the defects that the co-catalyst Methylaluminoxane (MAO) is expensive and large in dosage, the active center is easily deactivated by the action of a polar functional group, the copolymerization of olefin and a polar monomer cannot be catalyzed, the shape and the particle size of the polymer are difficult to control, and the like, are generally existed (for example, patent application No. 201310521144.7).
Claims (9)
1. A diimine palladium complex, wherein the diimine palladium complex has a structure represented by formula (I):
2. the process for preparing a diimine palladium complex (I) according to claim 1, which comprises the steps of:
(1) under the nitrogen atmosphere, trimethylaluminum is used for activating 2, 6-dipropylaniline, and then the trimethylaluminum and acenaphthenequinone are subjected to a ketone-amine condensation reaction to generate a diimine ligand;
(2) under the conditions of nitrogen atmosphere and room temperature, dissolving diimine ligand and (COD) PdMeCl in an organic solvent, and stirring for reaction for a period of time to obtain diimine palladium complex.
3. The process for preparing a diimine palladium complex (I) according to claim 2, which is characterized in that: in the step (1), the molar ratio of the 2, 6-dipropylaniline to the trimethylaluminum to the acenaphthenequinone is 1:1: 2.4.
4. The process for preparing a diimine palladium complex (I) according to claim 2, which is characterized in that: in step (1), the solvent used for the reaction is toluene.
5. The process for preparing a diimine palladium complex (I) according to claim 2, which is characterized in that: in step (2), the molar ratio of the diimine ligand to (COD) PdMeCl is 1: 1.2.
6. The process for preparing a diimine palladium complex (I) according to claim 2, which is characterized in that: in step (2), the organic solvent is dichloromethane.
7. The process for preparing a diimine palladium complex (I) according to claim 2, which is characterized in that: in the step (2), the reaction time is 8-12 hours.
8. Use of the diimine palladium complex (I) of claim 1 as a catalyst in the polymerization of 4-methyl-1-pentene.
9. The use according to claim 8, wherein the polymerization is carried out at a reaction pressure of 0.2 to 20 atm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114874365A (en) * | 2022-06-22 | 2022-08-09 | 宁夏清研高分子新材料有限公司 | Catalyst of TPX polymer and preparation method and application thereof |
| CN114920861A (en) * | 2022-06-22 | 2022-08-19 | 宁夏清研高分子新材料有限公司 | Catalyst and preparation method thereof, and preparation method of TPX polymer |
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| CN102250152A (en) * | 2011-05-26 | 2011-11-23 | 中山大学 | Preparation method and application of amido-imine nickel vinyl polymerization catalyst |
| CN105153239A (en) * | 2015-07-30 | 2015-12-16 | 中山大学 | Diamine nickel complex, and preparation method and application thereof |
| CN110317149A (en) * | 2019-07-31 | 2019-10-11 | 安徽大学 | Big steric hindrance flexibility diimide ligand, the diimine nickel based on it and palladium complex and its catalytic applications |
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Patent Citations (3)
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| CN102250152A (en) * | 2011-05-26 | 2011-11-23 | 中山大学 | Preparation method and application of amido-imine nickel vinyl polymerization catalyst |
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| Title |
|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114874365A (en) * | 2022-06-22 | 2022-08-09 | 宁夏清研高分子新材料有限公司 | Catalyst of TPX polymer and preparation method and application thereof |
| CN114920861A (en) * | 2022-06-22 | 2022-08-19 | 宁夏清研高分子新材料有限公司 | Catalyst and preparation method thereof, and preparation method of TPX polymer |
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Application publication date: 20210504 |