CN114874365B - Catalyst of TPX polymer and preparation method and application thereof - Google Patents
Catalyst of TPX polymer and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 229920000642 polymer Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000002466 imines Chemical class 0.000 claims abstract description 45
- 239000003446 ligand Substances 0.000 claims abstract description 32
- 125000004344 phenylpropyl group Chemical group 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 84
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 37
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 30
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- 238000006482 condensation reaction Methods 0.000 claims description 24
- 229920000306 polymethylpentene Polymers 0.000 claims description 24
- 239000011116 polymethylpentene Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229940078552 o-xylene Drugs 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003335 steric effect Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- CDZOGLJOFWFVOZ-UHFFFAOYSA-N n-propylaniline Chemical compound CCCNC1=CC=CC=C1 CDZOGLJOFWFVOZ-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910000071 diazene Inorganic materials 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- -1 diimine compound Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
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- 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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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention particularly relates to a catalyst of a TPX polymer, a preparation method and application thereof, belonging to the technical field of catalyst development, wherein the catalyst comprises the following raw materials: imine ligand and (COD) PdMeBr; wherein the raw materials of the imine ligand comprise a bidentate complex and an phenylpropyl group; the steric effect of the catalyst is improved by utilizing the characteristic of the phenylpropyl, so that the activity of the catalyst is improved, and the dosage of the catalyst is reduced.
Description
Technical Field
The invention belongs to the technical field of catalyst development, and particularly relates to a catalyst of a TPX polymer, and a preparation method and application thereof.
Background
Poly (4-methyl-1-pentene) has excellent characteristics of low density, high melting point, high transparency, low dielectric property, corrosion resistance and the like, has been widely applied in various fields, and the synthesis of a polymer (TPX polymer) based on isotactic poly (4-methyl-1-pentene) has been attracting more and more attention in recent decades, and the polymer is widely applied to industry as a UV transparent material. Isotactic poly (4-methyl-1-pentene) is an integral component of optical materials and films having high permeability to oxygen.
The existing catalysts for synthesizing TPX polymers are mainly Ziegler-Natta catalysts, transition metal catalysts and metallocene catalysts, which are expensive and have to be improved in catalyst activity.
Disclosure of Invention
The application aims to provide a catalyst of TPX polymer, a preparation method and application thereof, so as to solve the problem of low activity of the existing catalyst.
The embodiment of the invention provides a catalyst of TPX polymer, which comprises the following raw materials: imine ligand and (COD) PdMeBr; wherein the raw materials of the imine ligand comprise a bidentate complex and an phenylpropyl group.
Optionally, the raw materials of the catalyst comprise, in terms of mass: 1 part of an imine ligand and 2 parts of (COD) PdMeBr, wherein the raw materials of the imine ligand comprise, in terms of mass: 1 part of bidentate complex and 1 part of phenylpropyl.
Optionally, the chemical formula of the catalyst is:
wherein R is 1 Is o-xylene radical, R 2 Is a toluene group.
Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the catalyst of the TPX polymer, which comprises the following steps:
carrying out condensation reaction on the bidentate complex and the phenylpropyl to obtain an imine ligand;
mixing the imine ligand and (COD) PdMeBr in a solvent to perform a first reaction to obtain the catalyst.
Alternatively, the condensation reaction is carried out in the presence of aluminum chloride, the molar ratio of the bidentate complex, the phenylpropyl group and the aluminum chloride being 1:1:3.
Optionally, the time of the condensation reaction is 10-15h;
the solvent comprises at least one of benzene, dichloromethane and chloroform;
the time of the first reaction is 8-19h.
Based on the same inventive concept, embodiments of the present invention also provide the use of a catalyst of TPX polymer as described above, including the use of the catalyst for catalyzing the preparation of poly (4-methyl-1-pentene).
Optionally, the preparation of the poly (4-methyl-1-pentene) comprises:
mixing 4-methyl-1-pentene, a catalyst and a solvent for reaction, and then filtering and washing to obtain poly (4-methyl-1-pentene).
Optionally, the amount of material of the catalyst is less than the amount of material of the 4-methyl-1-pentene.
Alternatively, the amount of material of the catalyst is half the amount of material of the 4-methyl-1-pentene.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
the catalyst of the TPX polymer provided by the embodiment of the invention utilizes the characteristic of the phenylpropyl to improve the steric effect of the catalyst, so that the activity of the catalyst is improved, and the dosage of the catalyst is reduced.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present invention more readily apparent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flow chart of a method provided by an embodiment of the present invention.
Detailed Description
The advantages and various effects of the present invention will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the invention, not to limit the invention.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The technical scheme of the embodiment of the application aims to solve the technical problems, and the overall thought is as follows:
according to an exemplary embodiment of the present invention, there is provided a catalyst for TPX polymer, the raw materials of the catalyst comprising: imine ligand and (COD) PdMeBr; wherein the raw materials of the imine ligand comprise a bidentate complex and an phenylpropyl group.
In this embodiment, the bidentate complex has the following structural formula:
the structural formula of the phenylpropyl group is as follows:
the structural formula of the imine ligand is as follows:
in this example, the raw materials of the catalyst include, in terms of mass: 1 part of an imine ligand and 2 parts of (COD) PdMeBr, wherein the raw materials of the imine ligand comprise, in terms of mass: 1 part of bidentate complex and 1 part of phenylpropyl.
Specifically, the chemical formula of the catalyst is:
wherein R is 1 Is o-xylene radical, R 1 The structural formula is as follows:
R 2 is toluene group, R 2 The structure of (2) is as follows:
according to another exemplary embodiment of the present invention, there is provided a method for preparing a catalyst of TPX polymer as described above, the method comprising:
s1, performing condensation reaction on a bidentate complex and an phenylpropyl group to obtain an imine ligand;
specifically, in this example, the reaction flask was baked at high temperature to remove water vapor from the reaction flask, then the reaction flask was filled with nitrogen gas, and reacted in an oxygen-free atmosphere, and then a proper amount of bidentate complex was added to the reaction flask, and simultaneously a proper amount of aluminum chloride was added, and then a proper amount of phenylpropyl and bidentate complex was added to perform condensation reaction to obtain an imine ligand.
Wherein, bidentate complex: phenylpropyl: the molar ratio of aluminum chloride is 1:1:3, and the reaction time of the condensation reaction is 10-15 hours.
The reaction process of the above steps is as follows:
s2, mixing the imine ligand and (COD) PdMeBr in a solvent to perform a first reaction, thereby obtaining the catalyst.
Specifically, in this example, an appropriate amount of an imine ligand obtained by the condensation reaction and an appropriate amount of (COD) PdMeBr were added to a reaction flask under nitrogen atmosphere, a solvent was added to the reaction flask to carry out the second reaction, the reaction was carried out at room temperature for 13 hours, and then the solvent was evaporated by a rotary evaporation apparatus, and the obtained compound was precipitated with n-hexane to obtain an imine catalyst.
Wherein the solvent is at least one of benzene, dichloromethane and chloroform, preferably benzene. The molar ratio of imine ligand to (COD) PdMeBr was 1:2. The reaction time of the second reaction is 8-19 hours.
The reaction process of the above steps is as follows:
according to another exemplary embodiment of the present invention, there is provided the use of a catalyst for the preparation of poly (4-methyl-1-pentene) of a TPX polymer as described above.
In some embodiments, the preparation of poly (4-methyl-1-pentene) comprises:
s1, performing condensation reaction on a bidentate complex and an phenylpropyl group to obtain an imine ligand;
specifically, in this example, the reaction flask was baked at high temperature to remove water vapor from the reaction flask, then the reaction flask was filled with nitrogen gas, and reacted in an oxygen-free atmosphere, and then a proper amount of bidentate complex was added to the reaction flask, and simultaneously a proper amount of aluminum chloride was added, and then a proper amount of phenylpropyl and bidentate complex was added to perform condensation reaction to obtain an imine ligand.
Wherein, bidentate complex: phenylpropyl: the molar ratio of aluminum chloride is 1:1:3, and the reaction time of the condensation reaction is 10-15 hours.
The reaction process of the above steps is as follows:
s2, mixing the imine ligand and (COD) PdMeBr in a solvent to perform a first reaction, thereby obtaining the catalyst.
Specifically, in this example, an appropriate amount of an imine ligand obtained by the condensation reaction and an appropriate amount of (COD) PdMeBr were added to a reaction flask under nitrogen atmosphere, a solvent was added to the reaction flask to carry out the second reaction, the reaction was carried out at room temperature for 13 hours, and then the solvent was evaporated by a rotary evaporation apparatus, and the obtained compound was precipitated with n-hexane to obtain an imine catalyst.
Wherein the solvent is at least one of benzene, dichloromethane and chloroform, preferably benzene. The molar ratio of imine ligand to (COD) PdMeBr was 1:2. The reaction time of the second reaction is 8-19 hours.
The reaction process of the above steps is as follows:
s3, mixing 4-methyl-1-pentene, a catalyst and a solvent for reaction, and then filtering and washing to obtain poly (4-methyl-1-pentene).
Specifically, in this example, the reaction flask was purged with nitrogen after removing water vapor at high temperature, 5ml of 4-methyl-1-pentene and 5ml of benzene solution, 5umol of imine catalyst were added to the reaction flask, polymerization was stopped after 3 hours at 30 degrees celsius to obtain a polymer, and the polymer was filtered, then washed 3 times with ethanol, and dried to constant weight in a vacuum oven at 60 ℃.
Wherein the amount of material of the catalyst is less than the amount of material of the 4-methyl-1-pentene. Preferably, the amount of material of the catalyst is half the amount of material of said 4-methyl-1-pentene. The polymerization time is 2 to 8 hours, preferably 3 to 5 hours.
The catalyst of the present application, and the preparation method and application thereof will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
A method for preparing poly (4-methyl-1-pentene), comprising:
1. synthesis of catalyst
Removing water vapor of the reaction bottle by baking the reaction bottle at high temperature, filling nitrogen into the reaction bottle, adding 12mmol of propylaniline into the reaction bottle in an oxygen-free environment, simultaneously adding 12mL of aluminum chloride into the reaction bottle, setting the temperature to 135 ℃, reacting for 3 hours, then reducing the temperature to 25 ℃, and adding 12mmol of bidentate complex and propylaniline for condensation reaction. 0.5mmol of diimine compound obtained by condensation reaction, 0.5mmol of diimine compound and 0.6mmol (COD) of PdMeBr are added into a reaction bottle under nitrogen atmosphere, 20ml of methylene chloride is added into the reaction bottle as a solvent, the reaction is carried out for 12 hours at room temperature, then the solvent is evaporated by a rotary evaporation instrument, and the obtained compound is precipitated by n-hexane, thus obtaining the imine catalyst.
2. Synthesis of Poly (4-methyl-1-pentene)
The reaction flask was baked at high temperature to remove water vapor, then filled with nitrogen, 2ml of 4-methyl-1-pentene and 3ml of methylene chloride solution in an oxygen-free atmosphere, and 8umol of imine catalyst were added to the flask, and the reaction was stopped after polymerization at 30℃for 3 hours. The polymer was filtered and then washed 3 times with ethanol and dried to constant weight in a vacuum oven at 60 ℃.
Example 2
A method for preparing poly (4-methyl-1-pentene), comprising:
1. synthesis of catalyst
Removing water vapor of the reaction bottle by baking the reaction bottle at high temperature, filling nitrogen into the reaction bottle, adding 10mmol of propylaniline into the reaction bottle in an oxygen-free environment, simultaneously adding 30mL of aluminum chloride into the reaction bottle, setting the temperature to 120 ℃, reacting for 3 hours, then reducing the temperature to 25 ℃, and adding 10mmol of bidentate complex and propylaniline for condensation reaction. Adding 0.4mmol of diimine ligand obtained by condensation reaction, 0.4mmol of imine compound and 0.5mmol (COD) PdMeBr into a reaction bottle under nitrogen atmosphere, adding 20ml of methylene dichloride serving as a solvent into the reaction bottle, reacting for 12 hours at room temperature, then using a rotary evaporation instrument, evaporating the solvent, and precipitating the obtained compound by using normal hexane to obtain the diimine catalyst.
2. Synthesis of Poly (4-methyl-1-pentene)
The reaction flask was baked at high temperature to remove water vapor, then filled with nitrogen, 3ml of 4-methyl-1-pentene and 3ml of methylene chloride solution were added to the flask in an oxygen-free atmosphere, and 10umol of imine catalyst were added to the flask, and the reaction was stopped after polymerization at 30℃for 3 hours. The polymer was filtered and then washed 3 times with ethanol and dried to constant weight in a vacuum oven at 60 ℃.
Example 3
A method for preparing poly (4-methyl-1-pentene), comprising:
1. synthesis of catalyst
Removing water vapor of the reaction bottle by baking the reaction bottle at high temperature, filling nitrogen in the reaction bottle, adding 15mmol of propylaniline into the reaction bottle in an oxygen-free environment, simultaneously adding 13mL of aluminum chloride into the reaction bottle, setting the temperature to 120 ℃, reacting for 4 hours, then reducing the temperature to 25 ℃, and adding 5mmol of bidentate complex and propylaniline for condensation reaction. 0.5mmol of diimine ligand obtained by condensation reaction, 0.4mmol of imine compound and 0.5mmol (COD) of PdMeBr are added into a reaction bottle under nitrogen atmosphere, 20ml of methylene chloride is added into the reaction bottle for reaction, the reaction is carried out for 12 hours at room temperature, then a rotary evaporation instrument is used for evaporating the solvent, and the obtained compound is precipitated by n-hexane to obtain the imine compound.
2. Synthesis of Poly (4-methyl-1-pentene)
The reaction flask was baked at high temperature to remove water vapor, then filled with nitrogen, 4ml of 4-methyl-1-pentene and 3ml of methylene chloride solution in an oxygen-free atmosphere, and 12umol of imine catalyst were added to the flask, and the reaction was stopped after polymerization at 30℃for 3 hours. The polymer was filtered and then washed 3 times with ethanol and dried to constant weight in a vacuum oven at 60 ℃.
Example 4
A method for preparing poly (4-methyl-1-pentene), comprising:
1. synthesis of catalyst
Removing water vapor of the reaction bottle by baking the reaction bottle at high temperature, filling nitrogen into the reaction bottle, adding 15mmol of propylaniline into the reaction bottle in an oxygen-free environment, simultaneously adding 12mL of aluminum chloride into the reaction bottle, setting the temperature to 120 ℃, reacting for 3 hours, then reducing the temperature to 25 ℃, and adding 5mmol of bidentate complex and propylaniline for condensation reaction. 0.5mmol of diimine ligand obtained by condensation reaction, 0.5mmol of imine compound and 0.5mmol (COD) of PdMeCl are added into a reaction bottle under nitrogen atmosphere, 20ml of methylene chloride is added into the reaction bottle for reaction, the reaction is carried out for 12 hours at room temperature, then a rotary evaporation instrument is used for evaporating the solvent, and the obtained compound is precipitated by n-hexane to obtain the diimine palladium complex.
2. Synthesis of Poly (4-methyl-1-pentene)
The reaction flask was baked at high temperature to remove water vapor, then filled with nitrogen, 3ml of 4-methyl-1-pentene and 3ml of methylene chloride solution were added to the flask in an oxygen-free atmosphere, and 10umol of imine catalyst were added to the flask, and the reaction was stopped after polymerization at 30℃for 3 hours. The polymer was filtered and then washed 3 times with ethanol and dried to constant weight in a vacuum oven at 60 ℃.
Example 5
A method for preparing poly (4-methyl-1-pentene), comprising:
1. synthesis of catalyst
Removing water vapor of the reaction bottle by baking the reaction bottle at high temperature, filling nitrogen into the reaction bottle, adding 11mmol of propylaniline into the reaction bottle in an oxygen-free environment, simultaneously adding 11mL of aluminum chloride into the reaction bottle, setting the temperature to 120 ℃, reacting for 4 hours, then reducing the temperature to 25 ℃, and adding 5mmol of bidentate complex and propylaniline for condensation reaction. Adding 0.6mmol of imine compound obtained by condensation reaction, 0.6mmol of imine compound and 0.6mmol (COD) PdMeBr into a reaction bottle under nitrogen atmosphere, adding 20ml of methylene dichloride serving as a solvent into the reaction bottle, reacting for 12 hours at room temperature, then precipitating the obtained compound by n-hexane by using a rotary evaporation instrument, and obtaining the imine catalyst.
2. Synthesis of Poly (4-methyl-1-pentene)
The reaction flask was baked at high temperature to remove water vapor, then filled with nitrogen, 4ml of 4-methyl-1-pentene and 4ml of benzene solution were added to the flask in an oxygen-free atmosphere, and 10umol of imine catalyst was added to the flask to polymerize at 30℃for 3 hours, and then the reaction was stopped. The polymer was filtered and then washed 3 times with ethanol and dried to constant weight in a vacuum oven at 60 ℃.
Experimental example
The poly (4-methyl-1-pentene) prepared in examples 1-5 was tested for properties and the results are shown in the following table.
| Number average molecular weight | Molecular weight distribution | Degree of branching | |
| Example 1 | 12301g mol -1 | 1.32 | 155 |
| Example 2 | 13115g mol -1 | 1.26 | 144 |
| Example 3 | 15312g mol -1 | 1.34 | 146 |
| Example 4 | 13424g mol -1 | 1.28 | 154 |
| Example 5 | 15314g mol -1 | 1.33 | 153 |
As can be seen from the above table, the use of the catalysts provided in the examples herein to prepare poly (4-methyl-1-pentene) can result in higher polymer molecular weights.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
the catalyst provided by the embodiment of the invention improves the catalyst activity and reduces the dosage of the catalyst by improving the steric effect of the catalyst, and simultaneously can obtain higher polymer molecular weight, thereby reducing the reaction cost of the TPX material and improving the quality of the polymer.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (9)
1. A catalyst for TPX polymers, characterized in that the raw materials of the catalyst comprise: imine ligands
(COD) PdMeBr; wherein the raw materials of the imine ligand comprise a bidentate complex and an phenylpropyl group, and the chemical formula of the catalyst is as follows:
wherein R is 1 Is o-xylene radical, R 2 Is a toluene group.
2. A catalyst for TPX polymers according to claim 1, characterized in that the raw materials of the catalyst comprise, in terms of mass: 1 part of an imine ligand and 2 parts of (COD) PdMeBr, wherein the raw materials of the imine ligand comprise, in terms of mass: 1 part of bidentate complex and 1 part of phenylpropyl.
3. A process for preparing a catalyst for TPX polymers according to any one of claims 1 to 2, characterized in that it comprises:
carrying out condensation reaction on the bidentate complex and the phenylpropyl to obtain an imine ligand;
mixing the imine ligand and (COD) PdMeBr in a solvent to perform a first reaction to obtain the catalyst.
4. A process for the preparation of a catalyst for TPX polymers according to claim 3, characterized in that the condensation reaction is carried out in the presence of aluminium chloride, the molar ratio of bidentate complex, phenylpropyl and aluminium chloride being 1:1:3.
5. A process for the preparation of a catalyst for TPX polymers according to claim 3, characterized in that the time of the condensation reaction is 10-15 hours;
the solvent comprises at least one of benzene, dichloromethane and chloroform;
the time of the first reaction is 8-19h.
6. Use of a catalyst of a TPX polymer according to any of claims 1 to 2, wherein the use comprises using the catalyst for catalyzing the preparation of poly (4-methyl-1-pentene).
7. Use of a catalyst for TPX polymers according to claim 6, characterized in that the preparation of poly (4-methyl-1-pentene) comprises:
mixing 4-methyl-1-pentene, a catalyst and a solvent for reaction, and then filtering and washing to obtain poly (4-methyl-1-pentene).
8. Use of a catalyst for TPX polymers according to claim 7, characterized in that the amount of material of the catalyst is smaller than the amount of material of the 4-methyl-1-pentene.
9. Use of a catalyst for TPX polymers according to claim 8, characterized in that the amount of material of the catalyst is half the amount of material of the 4-methyl-1-pentene.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210712722.4A CN114874365B (en) | 2022-06-22 | 2022-06-22 | Catalyst of TPX polymer and preparation method and application thereof |
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