CN114736321A - Modified cyclic olefin copolymer in-kettle alloy and preparation method thereof - Google Patents

Modified cyclic olefin copolymer in-kettle alloy and preparation method thereof Download PDF

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CN114736321A
CN114736321A CN202210505665.2A CN202210505665A CN114736321A CN 114736321 A CN114736321 A CN 114736321A CN 202210505665 A CN202210505665 A CN 202210505665A CN 114736321 A CN114736321 A CN 114736321A
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ethylene
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norbornene
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CN114736321B (en
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潘莉
张湘汉
王峰
李悦生
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Tianjin University
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Abstract

The invention discloses a modified cyclic olefin copolymer in-kettle alloy and a preparation method thereof, and relates to the technical field of olefin copolymer synthesis. Specifically, the ethylene monomer and the cycloolefin monomer are adopted, and are copolymerized under the action of catalysts with different selectivity respectively, the generated copolymer solution is directly mixed according to the volume ratio, or the catalysts with different selectivity are directly mixed with the ethylene monomer and the cycloolefin monomer and then polymerized to obtain the polymer solution, and then the polymer solution is precipitated in the acidified ethanol solution to obtain the modified cycloolefin copolymer in-kettle alloy. The elongation at break of the prepared COC polymer in the kettle is variable within a certain range, the toughness can be greatly enhanced, the visible light transmittance is over 85 percent, the preparation method is simple, the steps of production and physical blending after subsequent separation are greatly simplified, and the preparation method has very important application prospect for modifying the COC polymer.

Description

Modified cyclic olefin copolymer in-kettle alloy and preparation method thereof
Technical Field
The invention relates to the technical field of olefin copolymer synthesis, in particular to a modified cyclic olefin copolymer in-kettle alloy and a preparation method thereof.
Background
Cyclic Olefin Copolymers (COC) are thermoplastic engineering plastics with high added value obtained by copolymerizing Cyclic olefins and alpha-olefins. It has important applications in optical materials, medical materials, packaging materials, etc. because the cycloolefin copolymer has advantages of high transparency, low birefringence, excellent heat resistance and chemical resistance, low dielectric constant, moisture barrier properties, and low water absorption rate.
The disadvantages of cycloolefin copolymers are mainly their poor toughness, their brittleness and, owing to their high thermal transition temperature, their poor processability, which limits their use to a certain extent. Chinese patent CN102731721 provides a cycloolefin copolymer and a preparation method thereof, by introducing a large-volume comonomer, the breaking strength and the breaking elongation of the cycloolefin copolymer are both improved, but the thermal transition temperature of the polymer obtained by the method is higher, which affects the application range of the polymer; chinese patent CN1106427 provides a modified cyclic olefin copolymer, which is modified by preparing a polymer blend material through melt extrusion, in such a way that the impact toughness and elongation at break of the cyclic olefin copolymer are improved; in the research of polyethylene resin, the processing performance of polyethylene with bimodal molecular weight distribution can be improved to a great extent by adjusting the molecular weight composition, and therefore, the Chinese patent CN105524217 provides a cycloolefin copolymer with bimodal molecular weight distribution and a preparation method thereof, the cycloolefin copolymer with bimodal distribution is prepared by a composite catalyst with a double active center and a solution polymerization method, the molecular weight distribution of the obtained cycloolefin copolymer is between 15 and 35, the processing fluidity is represented by a melt index, and the fluidity is found to be improved well, because the low molecular weight part in the cycloolefin copolymer with bimodal distribution can play a role of a plasticizer.
In summary, the preparation of polymer blend materials and the preparation of bimodal cycloolefin copolymers by physical or chemical blending modification are two methods capable of improving the processability and toughness of cycloolefin copolymers. While preparing polymer blend materials is a relatively simple and economical process. Most blending modifications are achieved by physical blending, the main methods of which are powder blending, melt blending, solution blending and emulsion blending. The solution blending method is to dissolve two or more polymers in a common solvent, stir and mix the two or more polymers uniformly, then evaporate the solvent or add a non-solvent to precipitate the two or more polymers together to obtain the polymer blending material, and the compatibility between the two or more polymers can be judged according to whether the polymer solution is layered or not and the transparency of the solution. The solution reaction blending method has the advantages of simple operation, low energy consumption compared with the melt blending, uniform mixing, excellent dispersion and the like. The COC polymer in-kettle alloy material with excellent comprehensive performance is prepared by directly carrying out solution reaction blending on the generated copolymer solution according to the volume ratio after copolymerization under the action of catalysts with different selectivity, and has very important application prospect for modifying COC polymers.
Disclosure of Invention
The invention aims to provide a modified cyclic olefin copolymer in-kettle alloy and a preparation method thereof, which are used for solving the problems in the prior art and further realizing the excellent performance of the cyclic olefin copolymer in-kettle alloy by adopting a simple preparation method.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a method for preparing a modified cycloolefin copolymer in-kettle alloy,
when stepwise copolymerization is adopted, the preparation method comprises the following steps:
1) under the conditions of no water and no oxygen and the existence of ethylene, sequentially adding an inert organic solvent, a cycloolefin monomer and a cocatalyst into a reaction system, then adding a main catalyst, and carrying out polymerization reaction on a cycloolefin copolymer to obtain a cycloolefin copolymer solution;
2) adopting a main catalyst with a structure different from that of the step 1), preparing a cycloolefin copolymer solution with insertion rate and molecular weight different from that of the step 1) according to the step 1), and then uniformly mixing two or more cycloolefin copolymer solutions;
3) adding the mixed solution obtained in the step 2) into an acidified ethanol solution for precipitation, washing and drying the obtained precipitate to obtain the alloy in the modified cyclic olefin copolymer kettle;
when synchronous copolymerization is adopted, the preparation method comprises the following steps:
a) under the conditions of no water and no oxygen and the existence of ethylene, sequentially adding an inert organic solvent, a cycloolefin monomer and a cocatalyst into a reaction system, then adding main catalysts with different structures, and carrying out polymerization reaction on a cycloolefin copolymer to obtain a cycloolefin copolymer solution;
b) adding the cycloolefin copolymer solution obtained in the step a) into an acidified ethanol solution for precipitation, washing and drying the obtained precipitate to obtain the modified cycloolefin copolymer in-kettle alloy;
the main catalyst is a metal complex catalyst with a structure shown in a formula (I) or a formula (II):
Figure BDA0003635892110000031
in the formula (I), when R is1When Ph, R2＝CF3Or CH3(ii) a When R is1When ═ thienyl, R2＝CF3(ii) a When R is1When it is furyl, R2＝CF3(ii) a When R is1＝CF3When R is2＝CH3(ii) a When R is1＝CH3When R is2＝CF3(ii) a Me is Ti, Zr or Hf;
in the formula (II), R3And R4Is hydrogen, alkyl or aryl.
In the modified cycloolefin copolymer solution obtained in the steps 1) and 2), the number average molecular weight of the copolymer is 20000-500000, the molecular weight distribution is 1.2-3.0, the insertion rate is 20-70%, and the glass transition temperature T isgAt 60-160 deg.C.
Further, the inert organic solvent is one or more of straight-chain hydrocarbon compounds, cyclic hydrocarbon compounds and aromatic hydrocarbon compounds.
Further, the cycloolefin monomer is one or more of norbornene, norbornadiene, dicyclopentadiene and dimethyloctahydronaphthalene.
Further, the cocatalyst is one or more of Methylaluminoxane (MAO), a mixture of triisobutylaluminum and tris (pentafluorophenyl) borane, a mixture of triisobutylaluminum and triphenylcarbenium tetrakis- (pentafluorophenyl) borate, and Modified Methylaluminoxane (MMAO) (CAS: 206451-54-9).
The Methylaluminoxane (MAO) may be methylaluminoxane powder (DMAO).
Further, the molar ratio of the cocatalyst to the main catalyst is 2000: 1-100: 1.
Further, the temperature of the polymerization reaction is 20-100 ℃, and the time is 1-20 min.
Further, in the steps 1) and 2), the ethylene pressure in the reaction system is 0.1-20 MPa.
Further, in the acidified ethanol solution, the acid is one or more of hydrochloric acid, sulfuric acid, phosphoric acid and formic acid.
Further, the volume ratio of the acid in the acidified ethanol solution is 10%.
In the step 2), the volume ratio of the two cycloolefin copolymer solutions is 10: 1-1: 10 when mixing; the ratio of the three cycloolefin copolymer solutions is 10:1: 1-1: 1:10 when mixing; the ratio of the four cycloolefin copolymer solutions is 10:1:1:1 to 1:1:1:10 when mixed, and so on.
The invention also provides the modified cyclic olefin copolymer in-kettle alloy prepared by the preparation method.
The invention discloses the following technical effects:
in the polymerization process, the catalyst with different cycloolefin monomer selectivity is used for respectively preparing cycloolefin copolymer solutions with different insertion rates and different molecular weights, and then the cycloolefin copolymer solutions are directly blended, or the catalysts with different selectivities are directly blended in the same reaction system for polymerization, so that the COC polymer in-kettle alloy material with uniformly dispersed components and excellent comprehensive performance is obtained. The elongation at break of the prepared COC polymer in the kettle is variable in a certain range, the visible light transmittance is more than 85%, the preparation method is simple, the steps of production and physical blending after subsequent separation are greatly simplified, and the preparation method has an important application prospect for modifying the COC polymer.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a Differential Scanning Calorimeter (DSC) two-shot temperature rise curve of ethylene/norbornene copolymers COC-1) and COC-2) in example 1 of the present invention;
FIG. 2 is a stress-strain curve of the alloy in the modified cycloolefin copolymer tank obtained in example 1 according to the present invention;
FIG. 3 is a Differential Scanning Calorimeter (DSC) two-shot temperature curve of ethylene/norbornene copolymer COC-1) and COC-2) in example 4 of the present invention;
FIG. 4 is a stress-strain curve of the alloy in the modified cycloolefin copolymer tank obtained in example 4 of the present invention;
FIG. 5 is a stress-strain curve of the alloy in the modified cycloolefin copolymer tank obtained in examples 5 to 7 according to the present invention;
FIG. 6 is a graph showing transmittance curves of the alloys in the modified cycloolefin copolymer tanks according to examples 1 to 4 of the present invention;
FIG. 7 is a GPC curve of the alloy in a modified cycloolefin copolymer tank according to example 7 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
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. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
In the following examples, a TA Q2000 type differential scanning calorimeter is used to measure the glass transition temperature of a polymer, the heating rate is 20 ℃/min, the cooling rate is 20 ℃/min, the scanning range is 30-200 ℃, and a secondary heating curve is adopted; an Instron 3369 type universal material testing machine is adopted to test the tensile mechanical property of the obtained polymer; the light transmittance of the polymer is measured at normal temperature by using an Shimadzu UV2700 visible-ultraviolet spectrophotometer; the molecular weight and the distribution of the polymer were measured by Agilent PL-GPC220 high temperature gel chromatography at 150 ℃ with 1,2, 4-trichlorobenzene as the mobile phase and 0.05 wt% of 2, 6-di-tert-butyl-4-methylphenol as an antioxidant at a flow rate of 1.0mL/min using PL EasiCal PS-1 as a standard.
Example 1
1) Under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 25mmol) and 1500 mu mol of Methylaluminoxane (MAO) are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added to carry out the copolymerization reaction of ethylene/norbornene, the copolymerization reaction time is 20min, the total volume of a reaction system is 30mL, and the ethylene/norbornene copolymer COC-1) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula I, wherein R1＝Ph，R2＝CF3；
(2) The molar ratio of MAO to the above-mentioned zirconium metal complex is 500: 1;
2) under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 90mmol) and 6000 mu mol of Methylaluminoxane (MAO) are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added to carry out the copolymerization reaction of ethylene/norbornene, the copolymerization reaction time is 10min, the total volume of a reaction system is 30mL, and the ethylene/norbornene copolymer COC-2) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula I, wherein R1＝Ph，R2＝CH3；
(2) The molar ratio of MAO to the above-mentioned zirconium metal complex was 2000: 1;
3) and (2) carrying out solution blending on the ethylene/norbornene copolymer solution prepared in the step 1) and the step 2) according to the volume ratio of 1:1, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
FIG. 1 is a Differential Scanning Calorimeter (DSC) two-shot temperature rise curve of ethylene/norbornene copolymers COC-1) and COC-2) in example 1. It can be seen from the figure that the ethylene/norbornene copolymer COC-1) has a lower glass transition temperature of 94.6 ℃ and a lower insertion rate for norbornene, the ethylene/norbornene copolymer COC-2) has a higher glass transition temperature of 152.7 ℃ and a higher insertion rate for norbornene, the insertion rate for norbornene in the examples being related to the amount of material added to norbornene during the copolymerization. By varying the amount of cocatalyst MAO, the polymers obtained have different molecular weights and distributions, which theoretically decrease and broaden as the amount of cocatalyst added increases due to the chain transfer reaction. The method realizes the in-kettle blending of the cycloolefin copolymer with different insertion rates and different molecular weights, obtains the in-kettle alloy of the cycloolefin copolymer with excellent performance, and simultaneously has variable elongation at break within a certain range.
FIG. 2 is a stress-strain curve of the alloy in the modified cycloolefin copolymer tank obtained in example 1. From the figure, it can be seen that the elongation at break is 4.5%.
Example 2
1) Under the anhydrous and anaerobic conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 25mmol) and 1500 mu mol of Modified Methylaluminoxane (MMAO) (CAS:206451-54-9) are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added for copolymerization of ethylene/norbornene, the copolymerization time is 20min, and the total volume of a reaction system is 30mL, so that an ethylene/norbornene copolymer COC-1) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula I, wherein R1Thienyl, R2＝CF3；
(2) The molar ratio of MMAO to the above-mentioned zirconium metal complex is 500: 1;
2) under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 90mmol) and 6000 mu mol of Modified Methylaluminoxane (MMAO) (CAS:206451-54-9) are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added for copolymerization of ethylene/norbornene, the copolymerization time is 10min, and the total volume of a reaction system is 30mL, so that an ethylene/norbornene copolymer COC-2) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula I, wherein R1Furyl, R2＝CF3；
(2) The molar ratio of MMAO to the above zirconium metal complex is 2000: 1;
3) and (2) carrying out solution blending on the ethylene/norbornene copolymer solution prepared in the step 1) and the step 2) according to the volume ratio of 2:1, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
Example 3
1) Under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 25mmol) and 1500 mu mol of methylaluminoxane powder (DMAO) are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added to carry out the copolymerization reaction of ethylene/norbornene, the copolymerization reaction time is 20min, and the total volume of a reaction system is 30mL, so that the ethylene/norbornene copolymer COC-1) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is ethyl;
(2) the molar ratio of DMAO to the above-described zirconium metal complex is 500: 1;
2) under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 90mmol) and 6000 mu mol of methylaluminoxane powder (DMAO) are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added to carry out the copolymerization reaction of ethylene/norbornene, the copolymerization reaction time is 10min, and the total volume of a reaction system is 30mL, so that the ethylene/norbornene copolymer COC-2) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is H;
(2) the molar ratio of DMAO to the above-described zirconium metal complex is 2000: 1;
3) and (3) carrying out solution blending on the ethylene/norbornene copolymer solution prepared in the step 1) and the step 2) according to the volume ratio of 1:2, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, carrying out suction filtration to obtain a filter cake, then washing the filter cake by using acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
Example 4
1) Under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 75mmol), 300 mu mol of triisobutylaluminum and 6 mu mol of triphenylcarbonium tetrakis (pentafluorophenyl) borate are sequentially added into a polymerization bottle, then 3 mu mol of titanium metal catalyst is added for copolymerization of ethylene/norbornene, the copolymerization time is 3min, and the total volume of a reaction system is 30mL, so that the ethylene/norbornene copolymer COC-1) solution is obtained, wherein the catalyst system comprises:
(1) titanium metal complexes of the molecular formula I, wherein R1＝CF3，R2＝CH3；
(2) The molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above titanium metal complex is 100:2: 1;
2) under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 25mmol), 600 mu mol of triisobutylaluminum and 6 mu mol of triphenylcarbonium tetrakis (pentafluorophenyl) borate are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added for copolymerization of ethylene/norbornene, the copolymerization time is 10min, and the total volume of a reaction system is 30mL, so that the ethylene/norbornene copolymer COC-2) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula I, wherein R1＝Ph，R2＝CF3；
(2) The molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above-described zirconium metal complex is 200:2: 1;
3) and (3) carrying out solution blending on the ethylene/norbornene copolymer solution prepared in the step 1) and the step 2) according to the volume ratio of 1:1, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, carrying out suction filtration to obtain a filter cake, then washing the filter cake by using acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
FIG. 3 is a Differential Scanning Calorimeter (DSC) two-shot temperature curve of ethylene/norbornene copolymers COC-1) and COC-2) of example 4. As can be seen from the figure, the COC-1) glass transition temperature of the ethylene/norbornene copolymer is higher and is 146.9 ℃, the insertion rate of the norbornene is higher, and the molecular weight is higher due to the low addition amount of triisobutyl aluminum; ethylene/norbornene copolymer COC-2) has a low glass transition temperature of 96.2 ℃ and a low insertion rate of norbornene, and has a low molecular weight due to a high amount of triisobutylaluminum; the in-kettle alloy of COC with high insertion rate and high molecular weight and COC with low insertion rate and low molecular weight is obtained by solution blending.
FIG. 4 is a stress-strain curve of the alloy in the modified cycloolefin copolymer tank obtained in example 4, and it was found in comparative example 1 that the elongation at break was increased from 4.5% to 14.5%, which is a large improvement.
Example 5
1) Under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 75mmol), 300 mu mol of triisobutylaluminum and 6 mu mol of tris (pentafluorophenyl) borane are sequentially added into a polymerization bottle, then 3 mu mol of titanium metal catalyst is added to carry out the copolymerization reaction of ethylene/norbornene, the copolymerization reaction time is 3min, and the total volume of a reaction system is 30mL, so that the ethylene/norbornene copolymer COC-1) solution is obtained, wherein the catalyst system comprises:
(1) titanium metal complexes of the molecular formula I, wherein R1Thienyl, R2＝CF3；
(2) The molar ratio of triisobutylaluminum and tris (pentafluorophenyl) borane to the titanium metal complex described above is 100:2: 1;
2) under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 25mmol), 600 mu mol of triisobutylaluminum and 6 mu mol of tris (pentafluorophenyl) borane are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added to carry out the copolymerization reaction of ethylene/norbornene, the copolymerization reaction time is 10min, and the total volume of a reaction system is 30mL, so that the ethylene/norbornene copolymer COC-2) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula I, wherein R1Furyl, R2＝CF3；
(2) The molar ratio of triisobutylaluminum and tris (pentafluorophenyl) borane to the above zirconium metal complex is 200:2: 1;
3) and (2) carrying out solution blending on the ethylene/norbornene copolymer solution prepared in the step 1) and the step 2) according to the volume ratio of 2:1, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
Example 6
1) Under the anhydrous and anaerobic conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is taken as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 75mmol) and 6000 mu mol of Methylaluminoxane (MAO) are sequentially added into a polymerization bottle, then 3 mu mol of titanium metal catalyst is added to carry out the copolymerization reaction of ethylene/norbornene, the copolymerization reaction time is 3min, the total volume of the reaction system is 30mL, and the ethylene/norbornene copolymer COC-1) solution is obtained, wherein the catalyst system comprises:
(1) titanium metal complexes of the molecular formula I, wherein R1Furyl, R2＝CF3；
(2) The molar ratio of MAO to the titanium metal complex described above was 2000: 1;
2) under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 25mmol) and 4500 mu mol of Methylaluminoxane (MAO) are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added to carry out the copolymerization reaction of ethylene/norbornene, the copolymerization reaction time is 10min, and the total volume of a reaction system is 30mL, so that the ethylene/norbornene copolymer COC-2) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula I, wherein R1Thienyl, R2＝CF3；
(2) The molar ratio of MAO to the above-described zirconium metal complex was 1500: 1;
3) and (2) carrying out solution blending on the ethylene/norbornene copolymer solution prepared in the step 1) and the step 2) according to the volume ratio of 1:2, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
Example 7
1) Under the anhydrous and anaerobic conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 90mmol) and 3000 mu mol of Modified Methylaluminoxane (MMAO) (CAS:206451-54-9) are sequentially added into a polymerization bottle, then 3 mu mol of titanium metal catalyst is added for copolymerization of ethylene/norbornene, the copolymerization time is 3min, and the total volume of a reaction system is 30mL, so that the ethylene/norbornene copolymer COC-1) solution is obtained, wherein the catalyst system comprises:
(1) titanium metal complexes of the molecular formula I, wherein R1＝Ph，R2＝CF3；
(2) The molar ratio of MMAO to the titanium metal complex is 1000: 1;
2) under the anhydrous and anaerobic conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.5MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 12mmol) and 3000 mu mol of Modified Methylaluminoxane (MMAO) (CAS:206451-54-9) are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added for copolymerization of ethylene/norbornene, the copolymerization time is 10min, and the total volume of a reaction system is 30mL, so that the ethylene/norbornene copolymer COC-2) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is H;
(2) the molar ratio of MMAO to the above-mentioned zirconium metal complex is 1000: 1;
3) and (2) carrying out solution blending on the ethylene/norbornene copolymer solution prepared in the step 1) and the step 2) according to the volume ratio of 1:1, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
Example 8
1) Under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.2MPa, toluene is used as a solvent, toluene, a toluene solution of norbornadiene (the amount of norbornadiene-containing substances is 90mmol), 3000 mu mol of methylaluminoxane powder (DMAO) are sequentially added into a polymerization bottle, 3 mu mol of titanium metal catalyst is added for copolymerization of ethylene/norbornadiene, the copolymerization time is 3min, and the total volume of a reaction system is 30mL, so that the ethylene/norbornadiene copolymer COC-1) solution is obtained, wherein the catalyst system comprises:
(1) molecular structural formulaA titanium metal complex of I, wherein R1＝Ph，R2＝CH3；
(2) The molar ratio of DMAO to the titanium metal complex is 1000: 1;
2) under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is taken as a solvent, toluene, a toluene solution of norbornadiene (the amount of the norbornadiene-containing substance is 12mmol) and 4500 mu mol of methylaluminoxane powder (DMAO) are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added to carry out the copolymerization reaction of ethylene/norbornadiene, the copolymerization reaction time is 10min, and the total volume of the reaction system is 30mL, so that the ethylene/norbornadiene copolymer COC-
2) A solution, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is phenyl;
(2) the molar ratio of DMAO to the above zirconium metal complex is 1500: 1;
3) and (2) carrying out solution blending on the ethylene/norbornadiene copolymer solution prepared in the step 1) and the step 2) according to the volume ratio of 2:1, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
Example 9
1) Under the anhydrous and anaerobic conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is taken as a solvent, toluene, a toluene solution of norbornadiene (the amount of the norbornadiene-containing substance is 90mmol), 300 mu mol of triisobutyl aluminum and 6 mu mol of triphenylcarbenium tetrakis (pentafluorophenyl) borate are sequentially added into a polymerization bottle, then 3 mu mol of titanium metal catalyst is added for copolymerization of ethylene/norbornadiene, the copolymerization time is 3min, and the total volume of a reaction system is 30mL, so as to obtain the ethylene/norbornadiene copolymer COC-1) solution, wherein the catalyst system comprises:
(1) titanium metal complexes of the molecular formula I, wherein R1＝Ph，R2＝CF3；
(2) The molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above titanium metal complex is 100:2: 1;
2) under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 5MPa, toluene is taken as a solvent, toluene, a toluene solution of norbornadiene (the amount of norbornadiene-containing substances is 12mmol), 600 mu mol of triisobutylaluminum and 6 mu mol of triphenylcarbenium tetrakis (pentafluorophenyl) borate are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added for copolymerization of ethylene/norbornadiene, the copolymerization time is 10min, and the total volume of a reaction system is 30mL, so that the ethylene/norbornadiene copolymer COC-2) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is ethyl;
(2) the molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above-described zirconium metal complex is 200:2: 1;
3) and (2) carrying out solution blending on the ethylene/norbornadiene copolymer solution prepared in the step 1) and the step 2) according to the volume ratio of 1:2, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
Example 10
1) Under the anhydrous and anaerobic conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is taken as a solvent, toluene, a toluene solution of dicyclopentadiene (the amount of substances containing dicyclopentadiene is 90mmol), 300 mu mol of triisobutyl aluminum and 6 mu mol of tris (pentafluorophenyl) borane are sequentially added into a polymerization bottle, then 3 mu mol of a titanium metal catalyst is added for copolymerization of ethylene/dicyclopentadiene, the copolymerization reaction time is 3min, and the total volume of a reaction system is 30mL, so as to obtain the ethylene/dicyclopentadiene copolymer COC-1) solution, wherein the catalyst system comprises:
(1) a titanium metal complex with a molecular structural formula I,wherein R is1Thienyl, R2＝CF3；
(2) The molar ratio of triisobutylaluminum and tris (pentafluorophenyl) borane to the titanium metal complex described above is 100:2: 1;
2) under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of dicyclopentadiene (the amount of substances containing dicyclopentadiene is 12mmol), 600 mu mol of triisobutylaluminum and 6 mu mol of tris (pentafluorophenyl) borane are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added for copolymerization of ethylene/dicyclopentadiene, the copolymerization reaction time is 10min, and the total volume of a reaction system is 30mL, so that the ethylene/dicyclopentadiene copolymer COC-2) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is hydrogen;
(2) the molar ratio of triisobutylaluminum and tris (pentafluorophenyl) borane to the above-described zirconium metal complex is 200:2: 1;
3) blending the ethylene/dicyclopentadiene copolymer solution prepared in the step 1) and the step 2) according to the volume ratio of 1:3, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, performing suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
Example 11
1) Under the anhydrous and oxygen-free conditions, the polymerization temperature is 75 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, 6mmol of dimethanonaphthalene, 600 mu mol of triisobutyl aluminum and 6 mu mol of triphenylcarbonium tetrakis (pentafluorophenyl) borate are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added to carry out copolymerization reaction of ethene/dimethanonaphthalene, the copolymerization reaction time is 10min, and the total volume of a reaction system is 30mL, so that the ethene/dimethanonaphthalene copolymer COC-1) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is phenyl;
(2) the molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above-described zirconium metal complex is 200:2: 1;
2) under the anhydrous and oxygen-free conditions, the polymerization temperature is 75 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, 30mmol of dimethano-octahydronaphthalene, 450 mu mol of triisobutyl aluminum and 6 mu mol of triphenylcarbon tetra (pentafluorophenyl) borate are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added to carry out copolymerization reaction of ethene/dimethano-octahydronaphthalene, the copolymerization reaction time is 10min, the total volume of a reaction system is 30mL, and the ethene/dimethano-octahydronaphthalene copolymer COC-2) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is H;
(2) the molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above-described zirconium metal complex is 150:2: 1;
3) and (2) carrying out solution blending on the ethylene/dimethylocta-hydrogen naphthalene copolymer solution prepared in the step 1) and the step 2) according to the volume ratio of 1:3, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
Example 12
1) Under the anhydrous and oxygen-free conditions, the polymerization temperature is 75 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, 30mmol of dimethanonaphthalene, 900 mu mol of triisobutyl aluminum and 6 mu mol of triphenylcarbenium tetrakis (pentafluorophenyl) borate are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added to carry out copolymerization reaction of ethene/dimethanonaphthalene, the copolymerization reaction time is 10min, and the total volume of a reaction system is 30mL, so that the ethene/dimethanonaphthalene copolymer COC-1) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is phenyl;
(2) the molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above-described zirconium metal complex is 300:2: 1;
2) under the anhydrous and oxygen-free conditions, the polymerization temperature is 75 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, 15mmol of dimethano-bridged octahydronaphthalene, 300 mu mol of triisobutyl aluminum and 6 mu mol of triphenylcarbon tetra (pentafluorophenyl) borate are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added for copolymerization of ethene/dimethano-bridged octahydronaphthalene, the copolymerization time is 10min, and the total volume of a reaction system is 30mL, so that the ethene/dimethano-bridged octahydronaphthalene copolymer COC-2) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is ethyl;
(2) the molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above-described zirconium metal complex is 100:2: 1;
3) and (2) carrying out solution blending on the ethylene/dimethylocta-hydrogen naphthalene copolymer solution prepared in the step 1) and the step 2) according to the volume ratio of 1:1, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
Example 13
1) Under the anhydrous and anaerobic conditions, the polymerization temperature is 75 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, after toluene, 30mmol of dimethylbridge octahydronaphthalene, 900 mu mol of triisobutyl aluminum and 6 mu mol of triphenylcarbon tetra (pentafluorophenyl) borate are sequentially added into a polymerization bottle, 3 mu mol of zirconium metal catalyst is added for copolymerization of ethylene/dimethylbridge octahydronaphthalene, the copolymerization reaction time is 10min, and the total volume of a reaction system is 30mL, the ethylene/dimethylbridge octahydronaphthalene copolymer COC-1) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is phenyl;
(2) the molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above-described zirconium metal complex is 300:2: 1;
2) under the anhydrous and oxygen-free conditions, the polymerization temperature is 75 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, 15mmol of dimethano-bridged octahydronaphthalene, 300 mu mol of triisobutyl aluminum and 6 mu mol of triphenylcarbon tetra (pentafluorophenyl) borate are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added for copolymerization of ethene/dimethano-bridged octahydronaphthalene, the copolymerization time is 10min, and the total volume of a reaction system is 30mL, so that the ethene/dimethano-bridged octahydronaphthalene copolymer COC-2) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is ethyl;
(2) the molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above-described zirconium metal complex is 100:2: 1;
3) under the anhydrous and oxygen-free conditions, the polymerization temperature is 75 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, 24mmol of dimethylbridge octahydronaphthalene, 600 mu mol of triisobutyl aluminum and 6 mu mol of triphenylcarbon tetra (pentafluorophenyl) borate are sequentially added into a polymerization bottle, then 3 mu mol of zirconium metal catalyst is added to carry out copolymerization reaction of ethylene/dimethylbridge octahydronaphthalene, the copolymerization reaction time is 10min, and the total volume of a reaction system is 30mL, so that the ethylene/dimethylbridge octahydronaphthalene copolymer COC-3) solution is obtained, wherein the catalyst system comprises:
(1) zirconium metal complexes of the molecular formula II, wherein R3And R4Is ethyl;
(2) the molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above-described zirconium metal complex is 200:2: 1;
4) and (3) carrying out solution blending on the ethylene/dimethylbridge octahydronaphthalene copolymer solution prepared in the step 1), the step 2) and the step 3) according to the volume ratio of 1:1:1, pouring the mixed solution into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
FIG. 5 is a stress-strain curve of the alloy in the modified cycloolefin copolymer tank obtained in examples 5 to 7. As can be seen from the figure, the elongation at break of the alloy in the modified cyclic olefin copolymer kettle varies from 35% to 50%, from the former 4.5%, to 14.5%, to the present 35% to 50%, and has a certain degree of variation, which proves that the modified cyclic olefin copolymer kettle alloy with the elongation at break variable in a certain range can be prepared by the method; FIG. 6 is a light transmittance curve of the alloy in the modified cycloolefin copolymer reactor in examples 1 to 4, and it can be seen from the graph that the light transmittance of the alloy in the modified cycloolefin copolymer reactor is over 85%, wherein the transmittance is even over 90% in the visible light region of 500-800 nm. FIG. 7 is a GPC curve of the in-pot alloy of the modified cycloolefin copolymer obtained in example 7. It can be seen from the figure that the molecular weight and the distribution thereof present a bimodal distribution, and the peak intensities of both are also equivalent, because the mixing of both at a ratio of 1:1, the low molecular weight fraction can act as a plasticizer, and at the same time can toughen the cycloolefin copolymer, so that the elongation at break is also higher, which can be up to 50% or more.
Example 14
1) Under the anhydrous and oxygen-free conditions, the polymerization temperature is 25 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 75mmol), 600 mu mol of triisobutylaluminum and 12 mu mol of triphenylcarbenium tetrakis (pentafluorophenyl) borate are sequentially added into a polymerization bottle, 3 mu mol of titanium metal catalyst and 3 mu mol of zirconium metal catalyst are simultaneously added for copolymerization of ethylene/norbornene, the copolymerization time is 5min, and the total volume of a reaction system is 60mL, so as to obtain the ethylene/norbornene copolymer solution, wherein the catalyst system comprises:
(1) titanium metal complexes of the molecular formula I, wherein R1＝Ph，R2＝CF3；
(2) The molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above titanium metal complex is 200:4: 1;
(3) molecular structureA zirconium metal complex of the formula II wherein R3＝R4＝CH3；
(4) The molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the above-described zirconium metal complex is 200:4: 1;
2) pouring the ethylene/norbornene copolymer solution prepared in the step 1) into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, performing suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
Example 15
1) Under the anhydrous and oxygen-free conditions, the polymerization temperature is 75 ℃, the ethylene pressure is 0.1MPa, toluene is used as a solvent, toluene, a toluene solution of norbornene (the amount of norbornene-containing substances is 80mmol), 600 mu mol of triisobutylaluminum and 12 mu mol of triphenylcarbenium tetrakis (pentafluorophenyl) borate are sequentially added into a polymerization bottle, 3 mu mol of titanium metal catalyst and 3 mu mol of titanium metal catalyst are simultaneously added for copolymerization of ethylene/norbornene, the copolymerization time is 5min, and the total volume of a reaction system is 60mL, so as to obtain the ethylene/norbornene copolymer solution, wherein the catalyst system comprises:
(1) titanium metal complexes of the molecular formula I, wherein R1＝Ph，R2＝CF3；
(2) The molar ratio of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate to the total amount of the above-described catalyst was 100:2: 1;
(3) titanium metal complexes of the molecular formula I, wherein R1＝CH3,R2＝CF3；
2) Pouring the ethylene/norbornene copolymer solution prepared in the step 1) into an ethanol solution containing 10% (volume ratio) hydrochloric acid for precipitation, performing suction filtration to obtain a filter cake, washing the filter cake with acetone, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the modified cyclic olefin copolymer in-kettle alloy.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (10)

1. A preparation method of a modified cycloolefin copolymer in-kettle alloy is characterized by comprising the following steps when fractional copolymerization is adopted:
1) under the conditions of no water and no oxygen and the existence of ethylene, sequentially adding an inert organic solvent, a cycloolefin monomer and a cocatalyst into a reaction system, then adding a main catalyst, and carrying out polymerization reaction on a cycloolefin copolymer to obtain a cycloolefin copolymer solution;
2) adopting a main catalyst with a structure different from that of the step 1), preparing a cycloolefin copolymer solution with insertion rate and molecular weight different from that of the step 1) according to the step 1), and then uniformly mixing two or more cycloolefin copolymer solutions;
3) adding the mixed solution obtained in the step 2) into an acidified ethanol solution for precipitation, washing and drying the obtained precipitate to obtain the alloy in the modified cyclic olefin copolymer kettle;
when synchronous copolymerization is adopted, the preparation method comprises the following steps:
a) under the conditions of no water and no oxygen and the existence of ethylene, sequentially adding an inert organic solvent, a cycloolefin monomer and a cocatalyst into a reaction system, then adding main catalysts with different structures, and carrying out polymerization reaction on a cycloolefin copolymer to obtain a cycloolefin copolymer solution;
b) adding the cycloolefin copolymer solution obtained in the step a) into an acidified ethanol solution for precipitation, washing and drying the obtained precipitate to obtain the modified cycloolefin copolymer in-kettle alloy;
the main catalyst is a metal complex catalyst with a structure shown in a formula (I) or a formula (II):
Figure FDA0003635892100000011
in the formula (I), when R1When Ph, R2＝CF3Or CH3(ii) a When R is1When ═ thienyl, R2＝CF3(ii) a When R is1When it is furyl, R2＝CF3(ii) a When R is1＝CF3When R is2＝CH3(ii) a When R is1＝CH3When R is2＝CF3Me is Ti, Zr or Hf;
in the formula (II), R3And R4Is hydrogen, alkyl or aryl.
2. The method according to claim 1, wherein the inert organic solvent is one or more of a linear hydrocarbon compound, a cyclic hydrocarbon compound and an aromatic hydrocarbon compound.
3. The method according to claim 1, wherein the cyclic olefin monomer is one or more of norbornene, norbornadiene, dicyclopentadiene, and dimethyloctahydronaphthalene.
4. The method of claim 1, wherein the cocatalyst is one or more of methylalumoxane, a mixture of triisobutylaluminum and tris (pentafluorophenyl) borane, a mixture of triisobutylaluminum and triphenylcarbenium tetrakis- (pentafluorophenyl) borate, and modified methylalumoxane.
5. The preparation method according to claim 1, wherein the molar ratio of the cocatalyst to the main catalyst is 2000:1 to 100: 1.
6. The method according to claim 1, wherein the polymerization reaction is carried out at a temperature of 20 to 100 ℃ for 1 to 20 min.
7. The preparation method according to claim 1, wherein in the steps 1) and 2), the ethylene pressure in the reaction system is 0.1-20 MPa.
8. The method according to claim 1, wherein the acid is one or more of hydrochloric acid, sulfuric acid, phosphoric acid and formic acid in the acidified ethanol solution.
9. The method according to claim 1, wherein the acid is present in the acidified ethanol solution in an amount of 10% by volume.
10. The modified cycloolefin copolymer in-tank alloy prepared by the production method as claimed in any one of claims 1 to 9.
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CN115947892A (en) * 2022-11-30 2023-04-11 宁夏清研高分子新材料有限公司 high-Tg high-temperature-resistant COC material and preparation method thereof
CN115947892B (en) * 2022-11-30 2024-03-12 宁夏清研高分子新材料有限公司 high-Tg high-temperature-resistant COC material and preparation method thereof

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