CN115850548A - Preparation method of cycloolefin copolymer - Google Patents

Preparation method of cycloolefin copolymer Download PDF

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CN115850548A
CN115850548A CN202211514298.9A CN202211514298A CN115850548A CN 115850548 A CN115850548 A CN 115850548A CN 202211514298 A CN202211514298 A CN 202211514298A CN 115850548 A CN115850548 A CN 115850548A
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lithium
cycloolefin
trichloride
rare earth
cycloolefin copolymer
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张光程
李全
郭方
李国华
刘新安
谷新春
何晓昶
王刚
张丽云
王文娟
李新
李浩博
孙艺蕾
孙林
袁小建
张瑜亮
柴新刚
李军波
崔莹
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SEDIN NINGBO ENGINEERING CO LTD
Dalian University of Technology
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SEDIN NINGBO ENGINEERING CO LTD
Dalian University of Technology
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Abstract

The invention discloses a preparation method of a cycloolefin copolymer, which is characterized by comprising the following steps: under the protection of inert gas nitrogen or argon, adding a cycloolefin monomer and an organic solvent into a dry oxygen-removed polymerization reactor, controlling the concentration of the cycloolefin monomer to be 0.5-2.0 mol/L, stirring and heating to the polymerization temperature of 25-80 ℃, then replacing a reaction system with an anhydrous and oxygen-free normal-pressure ethylene atmosphere, mixing and reacting a rare earth organic metal catalyst and an equimolar organic boron reagent in the solvent, then injecting the mixture into the reaction system, reacting for 5 minutes to 1 hour, and then carrying out termination reaction, glue precipitation, washing and drying to obtain the cycloolefin copolymer.

Description

Preparation method of cycloolefin copolymer
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a cyclic olefin copolymer.
Background
Cycloolefin copolymer (COC), an amorphous thermoplastic polymer material copolymerized from alpha-olefin and cycloolefin, has excellent properties such as high light transmission, high heat resistance, corrosion resistance, scratch resistance, low dielectric constant, low water absorption and ultraviolet resistance. As one of the high-end products of C5 series comprehensive utilization, COC is expected to replace other transparent resins such as polycarbonate, polymethyl methacrylate and the like to become more ideal optical materials. In addition, the COC material has the characteristics of high water vapor barrier, excellent biocompatibility and the like, and is widely applied to the fields of medical equipment and medicine packaging. The cyclic polyolefin is listed in the national key medical and epidemic prevention material direction key research and development plan. With the progress of COC synthesis technology in recent years, the production process is continuously perfected, the application field is continuously excavated, and COC materials have great development prospects in the aspects of medicine, packaging, electric appliances, automobiles, films, communication and the like.
The cycloolefin copolymers can be prepared by coordination-catalyzed copolymerization. In the sixty-seven decades of the last century, the copolymer of ethylene and monocyclic olefin was synthesized by Nata using Mg-Ti catalytic system, but the catalytic activity was very low. The copolymerization of cycloolefins has not made a major breakthrough until Methylaluminoxane (MAO) is successfully applied to the polymerization reaction and the catalytic activity is significantly improved. Compared with the traditional Mg-Ti catalyst, the metallocene catalyst has high catalytic activity, single structure and strong ligand adjustable property, and can realize the regulation and control of the performance of the cycloolefin copolymer. Since then, different types of catalyst systems such as metallocene organometallic catalysts, non-metallocene organometallic catalysts, late transition metal catalysts, etc. are continuously designed and improved, and the monomer structure of the cycloolefin copolymer is enriched more and more. Commercial cycloolefin copolymers (TOPAS and APEL) are currently synthesized predominantly using Norbornene (NB) or Tetracyclododecene (TCD) as comonomers.
In organometallic catalyst systems for the copolymerization of ethylene and cycloolefins, the structure of the catalyst and the corresponding polymerization process conditions have a significant influence on the catalytic activity and comonomer content. After the polar ligand is introduced into the single-metallocene organic metal catalyst, the activity of catalyzing the copolymerization reaction of the cycloolefin can be greatly improved. Nomura topic group finds that among polar ligands with different structures such as phenoxy ligand, imidazole ring imine ligand, pyrazole ring ligand and the like, the catalyst containing phenoxy ligand shows good copolymerization activity, the copolymerization catalytic activity and the steric hindrance of substituent groups on cyclopentadiene rings show obvious negative correlation, and when the steric hindrance of substituent groups on cyclopentadiene rings is larger, the copolymerization activity of the catalyst is lower. In document polym. Chem., 2018, 9, 4492-4497, authors synthesized fluorenylaminodimethyltitanium complexes with different steric hindrance and electronic effect by changing the substituents on the fluorene ring or amine group, and catalyzed copolymerization of ethylene and norbornene using Modified Methylaluminoxane (MMAO) as cocatalyst at 0 to 20 ℃. Although the steric hindrance around the cationic titanium center is significantly increased by the substituent on the amine-based ligand, the insertion rate of the norbornene monomer is reduced. However, the catalyst also realizes high copolymerization activity (up to 1620 kg/(mol. H)) of ethylene and norbornene at a relatively low temperature of 0 ℃. However, when the above-mentioned catalyst system is used in copolymerization, the amount of cocatalyst used is too high, which is not suitable for industrial application, and further reduction of the amount of MAO is required in follow-up research. In addition, a large amount of aluminum compound remains in the copolymerization product, and also affects the optical properties thereof. Therefore, how to regulate the steric hindrance and the electronic structure of the metallocene organometallic catalyst and realize high copolymerization activity under the condition of not adding MAO has important practical significance and practical value for improving and promoting the process of preparing COC by copolymerizing ethylene and cycloolefin.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a cycloolefin copolymer, which can effectively adjust the polymerization activity, the molecular weight distribution and the physical parameters of the copolymer by controlling the structure of a catalyst and the reaction conditions.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for preparing a cycloolefin copolymer, comprising the steps of: in the presence of inert gas such as nitrogen or argonUnder protection, adding a cycloolefin monomer and an organic solvent into a dry oxygen-removing polymerization reactor, controlling the concentration of the cycloolefin monomer to be 0.5-2.0 mol/L, stirring and heating to the polymerization temperature of 25-80 ℃, replacing a reaction system with an anhydrous and oxygen-free normal-pressure ethylene atmosphere, mixing and reacting a rare earth organic metal catalyst and an equimolar organic boron reagent in the solvent, injecting the mixture into the reaction system, reacting for 5 minutes to 1 hour, and then carrying out termination reaction, glue precipitation, washing and drying to obtain a cycloolefin copolymer, wherein the content of ethylene in the cycloolefin copolymer is 20-80 percent, the content of cycloolefin is 20-70 percent, the content of functionalized cycloolefin is 0-20 percent, and the number average molecular weight is 4 multiplied by 10 to obtain the cycloolefin copolymer 4 ~30×10 4 。
Preferably, the cyclic olefin is selected from the group consisting of norbornene, norbornadiene, dicyclopentadiene, 1, 3-cyclohexadiene, tetracyclododecene, 8-methyl-tetracyclododecene, 8-ethyl-tetracyclododecene.
Preferably, the functionalized cycloolefin has the structure shown below,
Figure SMS_1
wherein FG is selected from the group consisting of halogen, silyl, amino, pyrrolidinyl, piperidinyl, alkylphosphine, phosphoheterocycloalkyl, phosphacyclohexyl, siloxane or thiolate.
Preferably, the organic solvent is selected from one or a mixture of more than two of n-hexane, cyclohexane, n-heptane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene and trichlorobenzene.
Preferably, the concentration of the rare earth organic metal catalyst is 2.5X 10 5 ~1×10 4 mol/L, the organoboron reagent is selected from [ Ph 3 C][B(C 6 F 5 ) 4 ]、 [PhMe 2 NH][B(C 6 F 5 ) 4 ]、[HNMe(C 18 H 37 ) 2 ][B(C 6 F 5 ) 4 ]、B(C 6 F 5 ) 3 One or a mixture of several of them.
Preferably, the preparation method of the rare earth organic metal catalyst comprises the following steps: reacting a metallocene ligand with alkyl lithium in the solvent to obtain a ligand lithium salt, then adding the ligand lithium salt into anhydrous rare earth chloride for reaction, finally adding alkyl lithium or alkyl magnesium halide solution for reaction, and removing the solvent to obtain the rare earth organic metal catalyst.
Preferably, the anhydrous rare earth chloride is scandium trichloride, yttrium trichloride, lutetium trichloride, neodymium trichloride, holmium trichloride, samarium trichloride, gadolinium trichloride, ytterbium trichloride, europium trichloride or lanthanum trichloride.
Preferably, the metallocene ligand is selected from one of cyclopentadienyl, indenyl and fluorenyl ligands containing an optional substituent.
Preferably, the solvent includes tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydrothiophene, tetrahydropyran, tetramethylethylenediamine and 1, 2-dimethoxyethane.
Preferably, the alkyllithium is selected from at least one of methyllithium, ethyllithium, propyllithium, isopropyllithium, N-butyllithium, sec-butyllithium, pentyllithium, hexyllithium, cyclohexyllithium, N-eicosyllithium, phenyllithium, naphthyllithium, trimethylsilylmethyllithium and N, N-dimethylbenzyllithium; the alkyl magnesium halide is selected from at least one of methyl magnesium bromide, ethyl magnesium bromide, allyl magnesium bromide, cycloheptyl magnesium bromide, n-butyl magnesium bromide, ethyl magnesium chloride, isopropyl magnesium chloride and 2-methylbutyl magnesium chloride.
Compared with the prior art, the invention has the advantages that: the invention discloses a preparation method of a cyclic olefin copolymer, which is a binary and ternary copolymer prepared by catalyzing copolymerization of ethylene, cyclic olefin and functionalized cyclic olefin through a simply prepared rare earth catalyst, wherein the content of the cyclic olefin is 20-60 percent, the content of the functionalized cyclic olefin is 2-20 percent, and the number average molecular weight is 4 multiplied by 10 4 ~30×10 4 . The rare earth organic metal catalyst prepared by the simple method does not need complex separation and purification, has high yield, low cost and high activity and selectivity for catalyzing the copolymerization of ethylene and cycloolefin, and obtains the cycloolefin copolymer with unique structure and excellent performance; by varying the catalysisThe structure of the organic ligand and the type of the rare earth metal in the agent can effectively adjust the molecular weight of the cycloolefin copolymer, the insertion rate of the cycloolefin monomer and the thermal property; the molecular weight of the cycloolefin copolymer, the insertion rate of the cycloolefin monomers and the thermal properties can be accurately regulated and controlled by changing the dosage of the catalyst, the concentration of the cycloolefin monomers and the reaction conditions.
Drawings
FIG. 1 shows a rare earth scandium organometallic catalyst prepared in example 1 1 H-NMR chart;
FIG. 2 is a drawing showing a process for preparing an ethylene-norbornene copolymer according to example 4 1 H-NMR chart;
FIG. 3 is a drawing showing a preparation of an ethylene-norbornene copolymer prepared in example 4 1 C-NMR chart;
FIG. 4 is a GPC curve of an ethylene-norbornene copolymer prepared in example 7;
FIG. 5 is a DSC curve of the ethylene-norbornene copolymer prepared in example 7.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
The following examples are presented as further illustrations and are not intended to limit the scope of the claims. By nuclear magnetic resonance carbon spectrum ( 1 H-、 13 C-NMR), the molecular weight and molecular weight distribution index (ratio of weight average molecular weight to number average molecular weight) of the polymer were measured by Gel Permeation Chromatography (GPC), and the glass transition temperature (T) of the polymer was measured by differential thermal scanner (DSC) g ) And melting point (T) m ）。
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
A method for preparing a cycloolefin copolymer, comprising the steps of: under the protection of inert gas nitrogen or argon, adding a cycloolefin monomer and an organic solvent into a dry oxygen-removed polymerization reactor, controlling the concentration of the cycloolefin monomer to be 0.5-2.0 mol/L, stirring and heating to the polymerization temperature of 25-80 ℃, replacing a reaction system with an anhydrous and oxygen-free normal-pressure ethylene atmosphere, and carrying out rare earth organic goldMixing a catalyst and an equimolar organic boron reagent in a solvent for reaction, injecting the mixture into a reaction system, reacting for 5 minutes to 1 hour, terminating the reaction, precipitating glue, washing and drying to obtain the cyclic olefin copolymer, wherein the content of ethylene in the cyclic olefin copolymer is 20-80 percent, the content of cyclic olefin is 20-70 percent, the content of functionalized cyclic olefin is 0-20 percent, and the number average molecular weight is 4 multiplied by 10 4 ~30×10 4 。
The cycloolefin is at least one selected from norbornene, norbornadiene, dicyclopentadiene, 1, 3-cyclohexadiene, tetracyclododecene, 8-methyl-tetracyclododecene and 8-ethyl-tetracyclododecene. The structure of the functionalized cycloolefin is shown below,
Figure SMS_2
wherein FG is selected from the group consisting of halogen, silyl, amino, pyrrolidinyl, piperidinyl, alkylphosphine, phosphoheterocycloalkyl, phosphacyclohexyl, siloxane or thiolate. The organic solvent is selected from one or more of n-hexane, cyclohexane, n-heptane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene and trichlorobenzene. The organoboron reagent being selected from [ Ph 3 C][B(C 6 F 5 ) 4 ]、 [PhMe 2 NH][B(C 6 F 5 ) 4 ]、[HNMe(C 18 H 37 ) 2 ][B(C 6 F 5 ) 4 ]、B(C 6 F 5 ) 3 One or a mixture of several of them.
The concentration of the above rare earth organometallic catalyst is 2.5X 10 5 ~1×10 4 The preparation method of the rare earth organic metal catalyst comprises the following steps: reacting a metallocene ligand with alkyl lithium in a solvent to obtain a ligand lithium salt, then adding the ligand lithium salt into anhydrous rare earth chloride for reaction, finally adding alkyl lithium or alkyl magnesium halide solution for reaction, and removing the solvent to obtain the rare earth organic metal catalyst. Wherein the anhydrous rare earth chloride is scandium trichloride, yttrium trichloride, lutetium trichloride, neodymium trichloride, holmium trichloride, samarium trichloride, gadolinium trichloride, ytterbium trichloride, europium trichloride or trichloro-chlorineAnd (4) lanthanum melting. The metallocene ligand is selected from one of cyclopentadienyl, indenyl and fluorenyl ligands containing any substituent. The solvent includes tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydrothiophene, tetrahydropyran, tetramethylethylenediamine and 1, 2-dimethoxyethane. The alkyllithium is selected from at least one of methyllithium, ethyllithium, propyllithium, isopropyllithium, N-butyllithium, sec-butyllithium, pentyllithium, hexyllithium, cyclohexyllithium, N-eicosyllithium, phenyllithium, naphthyllithium, trimethylsilylmethylene lithium and N, N-dimethylbenzyllithium; the alkyl magnesium halide is at least one selected from the group consisting of methyl magnesium bromide, ethyl magnesium bromide, allyl magnesium bromide, cycloheptyl magnesium bromide, n-butyl magnesium bromide, ethyl magnesium chloride, isopropyl magnesium chloride and 2-methylbutyl magnesium chloride.
Example 1
1. Preparation of lithium (2, 3,4, 5-tetramethyl-2, 4-cyclopentadien-1-yl) silane salt
2.004 g (10 mmol) of trimethyl (2, 3,4, 5-tetramethyl-2, 4-cyclopentadien-1-yl) silane C are dissolved in 10 mL of tetrahydrofuran under an inert atmosphere of anhydrous and oxygen-free 5 Me 4 SiMe 3 After H, cooling to-30 ℃, dropwise adding 4 mL (10 mmol) of 2.5 mol/L n-BuLi n-hexane solution while stirring, heating to room temperature, and reacting for 30 min to obtain C 5 Me 4 SiMe 3 And (3) Li solution.
2. Preparation of rare earth scandium-trimethylsilylmethyl organometallic catalyst
Under an inert atmosphere of anhydrous oxygen-free, 1.513 g (10 mmol) of anhydrous ScCl is weighed 3 Heating in 20 mL of tetrahydrofuran at 80 deg.C, stirring for 12 h, cooling to room temperature, and adding dropwise C prepared above while stirring 5 Me 4 SiMe 3 Reacting the Li solution at room temperature for 1 h; 1.812 g (20 mmol) of trimethylsilyllithium LiCH were weighed 2 SiMe 3 Dissolving in 18 mL of tetrahydrofuran, stirring, dropwise adding into the scandium solution, continuously reacting for 3 h at room temperature, and vacuumizing to remove the solvent to obtain the rare earth organic metal catalyst with the yield of 99%. FIG. 1 shows preparation of rare earth scandium organometallic catalyst 1 H-NMR chart. 1 H NMR (C 6 D 6 , 25 ℃) : δ = -0.2 ppm (q, 4H, Sc-CH 2 SiMe 3 ) ; 0.31 ppm (s, 18H, Sc-CH 2 SiMe 3 ) ; 0.44 ppm (s, 9H, Si(CH 3 ) 3 ) ; 1.17 ppm (t, 4H, THF) ; 1.92 ppm (s, 6H, C 5 Me 4 ) ; 2.23 ppm (s, 6H, C 5 Me 4 ) ; 3.62 ppm (t, 4H, THF)。
3. Preparation of ethylene-norbornene copolymer
In a glove box, magnetons, 1.88g (20 mmol) of norbornene and 40 mL of toluene were charged into a 100 mL two-necked round-bottomed flask, the two-necked flask was sealed and taken out of the glove box, and connected to Schlenk and an ethylene branch, after replacing air, anhydrous and oxygen-free atmospheric pressure ethylene gas was introduced into the reaction system, and after stirring for 2 min, 1. Mu. Mol of the rare earth scandium-trimethylsilylmethyl organometallic catalyst prepared above and an equimolar amount of [ Ph ] 3 C][B(C 6 F 5 ) 4 ]2 mL of toluene solution was quickly added to the two-necked flask through a sealed needle, and polymerized at 25 ℃ for 5 min. Methanol was added to terminate the reaction, and the polymer was washed with methanol and dried under vacuum to obtain an ethylene-norbornene copolymer. The results of the polymer structure and property analysis are as follows: norbornene content 51% in terms of mole percentage, number average molecular weight 10.8X 10 4 Molecular weight distribution index (M) w /M n ) Is 1.75, glass transition temperature T g The temperature was 126 ℃.
Example 2
1. Preparation of rare earth scandium-N, N-dimethyl o-toluene organometallic catalyst
Under an inert atmosphere of anhydrous oxygen-free, 1.513 g (10 mmol) of anhydrous ScCl is weighed 3 Heating to 80 ℃ in 20 mL of tetrahydrofuran and stirring for 12 h, cooling to room temperature, and adding C prepared in step 1 of example 1 dropwise with stirring 5 Me 4 SiMe 3 Reacting the Li solution at room temperature for 1 h; weighing 2.700 g (20 mmol) of N, N-dimethyl o-toluidine, dissolving in 10 mL of tetrahydrofuran, then dropwise adding 8 mL (20 mmol) of 2.5 mol/L N-BuLi N-hexane solution for reacting for 1 h, dropwise adding the reaction solution into the scandium solution, continuing to react for 2 h at room temperature, and obtaining the rare earth organometallic catalyst after the solvent is pumped out in vacuum, wherein the yield is 98%.
2. Preparation of ethylene-norbornene copolymer
In a glove box, magnetons, 1.88g (20 mmol) of norbornene and 40 mL of toluene were charged into a 100 mL two-necked round-bottomed flask, the two-necked flask was sealed and taken out of the glove box, and connected to Schlenk and an ethylene branch, after replacing air, anhydrous oxygen-free atmospheric pressure ethylene gas was introduced into the reaction system, and after stirring for 2 min, 1. Mu. Mol of the above-prepared rare earth scandium-N, N-dimethyl-o-toluene organometallic catalyst and an equimolar amount of [ Ph ] were further added 3 C][B(C 6 F 5 ) 4 ]2 mL of toluene solution was quickly added to the two-necked flask through a sealed needle, and polymerized at 25 ℃ for 5 min. Methanol was added to terminate the reaction, and the polymer was washed with methanol and dried under vacuum to obtain an ethylene-norbornene copolymer. The results of the polymer structure and property analysis are as follows: norbornene content 26% in terms of mole percent, number average molecular weight 15.3X 10 4 Molecular weight distribution index (M) w /M n ) Is 1.81, glass transition temperature T g It was 44 ℃.
Example 3
1. Preparation of rare earth yttrium-trimethylsilylmethyl organic metal catalyst
Weighing 1.952 g (10 mmol) of anhydrous YCl under anhydrous and oxygen-free inert atmosphere 3 Heating to 80 ℃ in 20 mL of tetrahydrofuran and stirring for 12 h, cooling to room temperature, and adding C prepared in step 1 of example 1 dropwise with stirring 5 Me 4 SiMe 3 Reacting the Li solution at room temperature for 1 h; 1.812 g (20 mmol) of trimethylsilyllithium LiCH were weighed 2 SiMe 3 Dissolving in 18 mL of tetrahydrofuran, stirring, dropwise adding into the yttrium solution, continuously reacting for 3 h at room temperature, and vacuumizing to remove the solvent to obtain the rare earth organic metal catalyst with the yield of 99%.
2. Preparation of ethylene-norbornene copolymer
In a glove box, magnetons, 1.88g (20 mmol) of norbornene and 40 mL of toluene were charged into a 100 mL two-necked round-bottomed flask, the two-necked flask was sealed and taken out of the glove box, and connected to Schlenk and an ethylene branch, air was replaced, anhydrous and oxygen-free atmospheric ethylene gas was introduced into the reaction system, and stirred for 2 min, and 1. Mu. Mol of the above-prepared rare earth yttrium-trimethylsilylmethyl organometallic catalyst and the like were addedMolar amount of [ Ph 3 C][B(C 6 F 5 ) 4 ]2 mL of the toluene solution was quickly added to the two-necked flask through a sealed needle, and polymerized at 25 ℃ for 5 min. Methanol was added to terminate the reaction, and the polymer was washed with methanol and dried under vacuum to obtain an ethylene-norbornene copolymer. The results of the polymer structure and property analysis are as follows: norbornene content 41% in mol percent, number average molecular weight 28.2X 10 4 Molecular weight distribution index (M) w /M n ) Is 2.05, glass transition temperature T g The temperature was 110 ℃.
Example 4
1. Preparation of ethylene-norbornene copolymer
In a glove box, magnetons, 1.88g (20 mmol) of norbornene and 40 mL of toluene were charged into a 100 mL two-necked round-bottomed flask, the two-necked flask was sealed and taken out of the glove box, and connected to Schlenk and an ethylene branch, after replacing air, anhydrous oxygen-free atmospheric pressure ethylene gas was introduced into the reaction system, and after stirring for 2 min, 1. Mu. Mol of the catalyst prepared in step 2 of example 1 was mixed with an equimolar amount of [ Ph ] 3 C][B(C 6 F 5 ) 4 ]2 mL of the toluene solution was quickly added to the two-necked flask through a sealed needle, and polymerized at 70 ℃ for 5 min. Methanol was added to terminate the reaction, and the polymer was washed with methanol and dried under vacuum to obtain an ethylene-norbornene copolymer. The results of the polymer structure and property analysis are as follows: norbornene content 43% in mol percent, number average molecular weight 4.5X 10 4 Molecular weight distribution index (M) w /M n ) Is 2.21, glass transition temperature T g The temperature was 126 ℃. FIG. 2 is a diagram showing a method for preparing an ethylene-norbornene copolymer 1 H-NMR chart; 1 H NMR (C 2 D 2 Cl 4 0-3.0 ppm of hydrogen No. 1-9 at 100 ℃;
Figure SMS_3
。
FIG. 3 is a diagram of a process for preparing an ethylene-norbornene copolymer 1 C-NMR chart; 13 C NMR (C 2 D 2 Cl 4 at 100 ℃) 44.5-46.0 ppm is 2 andcarbon No. 3, carbon Nos. 1 and 4 at 39.0 to 40.3 ppm, carbon No. 7 at 30.9 ppm, and carbon Nos. 5,6,8, and 9 at 27.5 to 29.0 ppm.
Example 5
Preparation of ethylene-norbornene copolymer
In a glove box, magnetons, 2.82 g (30 mmol) of norbornene and 40 mL of toluene were charged into a 100 mL two-necked round-bottomed flask, the two-necked flask was sealed and taken out of the glove box, and connected to Schlenk and an ethylene branch, after replacing air, anhydrous oxygen-free atmospheric pressure ethylene gas was introduced into the reaction system, and after mixing and stirring for 2 min, 1. Mu. Mol of the catalyst prepared in step 2 of example 1 and an equimolar amount of [ Ph ] 3 C][B(C 6 F 5 ) 4 ]2 mL of toluene solution was quickly added to the two-necked flask through a sealed needle, and polymerized at 25 ℃ for 5 min. Methanol was added to terminate the reaction, and the polymer was washed with methanol and dried under vacuum to obtain an ethylene-norbornene copolymer. The results of the polymer structure and property analysis are as follows: norbornene content 41% in terms of mole percent, number average molecular weight 8.2X 10 4 Molecular weight distribution index (M) w /M n ) Is 2.09, glass transition temperature T g The temperature was 120 ℃.
Example 6
Preparation of ethylene-norbornene copolymer
In a glove box, magnetons, 3.76 g (40 mmol) of norbornene and 40 mL of toluene were charged into a 100 mL two-necked round-bottomed flask, the two-necked flask was sealed and taken out of the glove box, and connected to Schlenk and an ethylene branch, after replacing air, anhydrous oxygen-free atmospheric pressure ethylene gas was introduced into the reaction system, and after mixing and stirring for 2 min, 1. Mu. Mol of the catalyst prepared in step 2 of example 1 and an equimolar amount of [ Ph ] 3 C][B(C 6 F 5 ) 4 ]2 mL of toluene solution was quickly added to the two-necked flask through a sealed needle, and polymerized at 25 ℃ for 5 min. Methanol was added to terminate the reaction, and the polymer was washed with methanol and dried under vacuum to obtain an ethylene-norbornene copolymer. The results of the polymer structure and property analysis are as follows: norbornene content 40% in terms of mole percent, number average molecular weight 6.3X 10 4 Molecular weight distribution index (M) w /M n ) Is 1.94, glass transition temperature T g The temperature was 120 ℃.
Example 7
Preparation of ethylene-norbornene copolymer
In a glove box, magnetons, 1.88g (20 mmol) of norbornene and 20 mL of toluene were charged into a 100 mL two-necked round-bottomed flask, the two-necked flask was sealed and taken out of the glove box, and connected to Schlenk and an ethylene branch, after replacing air, anhydrous oxygen-free atmospheric pressure ethylene gas was introduced into the reaction system, and after mixing and stirring for 2 min, 1. Mu. Mol of the catalyst prepared in step 2 of example 1 and an equimolar amount of [ Ph ] were added 3 C][B(C 6 F 5 ) 4 ]2 mL of toluene solution was quickly added to the two-necked flask through a sealed needle, and polymerized at 25 ℃ for 5 min. Methanol was added to terminate the reaction, and the polymer was washed with methanol and dried under vacuum to obtain an ethylene-norbornene copolymer. The results of the polymer structure and property analysis are as follows: norbornene content 55% in terms of mole percent, FIG. 4 is a GPC curve of the ethylene-norbornene copolymer prepared, and it is possible to obtain a copolymer having a number average molecular weight of 7.2X 10 4 Molecular weight distribution index (M) w /M n ) At 1.89, FIG. 5 is a DSC curve of the ethylene-norbornene copolymer prepared, which can give the glass transition temperature T of the copolymer g The temperature was 139 ℃.
Example 8
Preparation of ethylene-norbornene copolymer
In a glove box, magnetons, 1.88g (20 mmol) of norbornene and 10 mL of toluene were charged into a 100 mL two-necked round-bottomed flask, the two-necked flask was sealed and taken out of the glove box, and connected to Schlenk and an ethylene branch, after replacing air, anhydrous oxygen-free atmospheric pressure ethylene gas was introduced into the reaction system, and after stirring for 2 min, 1. Mu. Mol of the catalyst prepared in step 2 of example 1 was mixed with an equimolar amount of [ Ph ] 3 C][B(C 6 F 5 ) 4 ]2 mL of the toluene solution was quickly added to the two-necked flask through a sealed needle, and polymerized at 25 ℃ for 5 min. Methanol was added to terminate the reaction, and the polymer was washed with methanol and dried under vacuum to obtain an ethylene-norbornene copolymer. The results of the polymer structure and property analysis are as follows: in mole percentA norbornene content of 49% in terms of fraction, and a number average molecular weight of 4.1X 10 4 Molecular weight distribution index (M) w /M n ) Is 2.05, glass transition temperature T g The temperature was 128 ℃.
Example 9
Preparation of ethylene-norbornene copolymer
In a glove box, magnetons, 1.88g (20 mmol) of norbornene and 20 mL of toluene were charged into a 100 mL two-necked round-bottomed flask, the two-necked flask was sealed and taken out of the glove box, and connected to Schlenk and an ethylene branch, after replacing air, anhydrous oxygen-free atmospheric pressure ethylene gas was introduced into the reaction system, and after stirring for 2 min, 10. Mu. Mol of the catalyst prepared in step 2 of example 1 and an equimolar amount of [ Ph ] were added 3 C][B(C 6 F 5 ) 4 ]2 mL of toluene solution was quickly added to the two-necked flask through a sealed needle, and polymerized at 25 ℃ for 5 min. Methanol was added to terminate the reaction, and the polymer was washed with methanol and dried under vacuum to obtain an ethylene-norbornene copolymer. The results of the polymer structure and property analysis are as follows: norbornene content 38% in terms of mole percent, number average molecular weight 12.1X 10 4 Molecular weight distribution index (M) w /M n ) Is 1.89, glass transition temperature T g The temperature was 94 ℃.
Example 10
Preparation of ethylene-tetracyclododecene copolymer
In a glove box, a magneton, 3.20 g (20 mmol) of tetracyclododecene and 40 mL of toluene were charged into a 100 mL two-necked round-bottomed flask, the two-necked flask was sealed and taken out of the glove box, and connected to a Schlenk and an ethylene branch, after replacing air, anhydrous oxygen-free atmospheric pressure ethylene gas was introduced into the reaction system, and after stirring for 2 min, 1. Mu. Mol of the catalyst prepared in step 2 of example 1 above was mixed with an equimolar amount of [ Ph ] 3 C][B(C 6 F 5 ) 4 ]2 mL of toluene solution was quickly added to the two-necked flask through a sealed needle, and polymerized at 25 ℃ for 5 min. The reaction was terminated by adding methanol, and the polymer was washed with methanol and dried under vacuum to obtain an ethylene-tetracyclododecene copolymer. The results of the polymer structure and property analysis are as follows: tetracyclododecanol in mole percentCarbene content 35%, number average molecular weight 10.6X 10 4 Molecular weight distribution index (M) w /M n ) Is 1.62, glass transition temperature T g The temperature was 170 ℃.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also appreciate that they may make various changes, modifications, additions and substitutions within the spirit and scope of the invention.

Claims (10)

1. A method for preparing a cycloolefin copolymer, characterized by comprising the steps of: under the protection of inert gas nitrogen or argon, adding a cycloolefin monomer and an organic solvent into a dry oxygen-removing polymerization reactor, controlling the concentration of the cycloolefin monomer to be 0.5-2.0 mol/L, stirring and heating to the polymerization temperature of 25-80 ℃, replacing a reaction system with an anhydrous and oxygen-free normal-pressure ethylene atmosphere, mixing and reacting a rare earth organic metal catalyst and an equimolar organic boron reagent in the solvent, injecting the mixture into the reaction system, reacting for 5 minutes to 1 hour, and then carrying out termination reaction, glue precipitation, washing and drying to obtain a cycloolefin copolymer, wherein the content of ethylene in the cycloolefin copolymer is 20-80 percent, the content of cycloolefin is 20-70 percent, the content of functionalized cycloolefin is 0-20 percent, and the number average molecular weight is 4 multiplied by 10 to obtain the cycloolefin copolymer 4 ~30×10 4 。
2. The method for producing a cycloolefin copolymer according to claim 1, characterized in that: the cycloolefin is selected from norbornene, norbornadiene, dicyclopentadiene, 1, 3-cyclohexadiene, tetracyclododecene, 8-methyl-tetracyclododecene, and 8-ethyl-tetracyclododecene.
3. The method for producing a cycloolefin copolymer according to claim 1, characterized in that: the structure of the functionalized cycloolefin is shown as follows,
Figure DEST_PATH_IMAGE001
wherein FG is selected from the group consisting of halogen, silyl, amino, pyrrolidinyl, piperidinyl, alkylphosphine, phosphoheterocycloalkyl, phosphacyclohexyl, siloxane or thiolate.
4. The method for preparing a cyclic olefin copolymer according to claim 1, wherein: the organic solvent is one or a mixture of more than two of n-hexane, cyclohexane, n-heptane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene and trichlorobenzene.
5. The method for producing a cycloolefin copolymer according to claim 1, characterized in that: the concentration of the rare earth organic metal catalyst is 2.5 multiplied by 10 5 ~1×10 4 mol/L, the organoboron reagent is selected from [ Ph 3 C][B(C 6 F 5 ) 4 ]、 [PhMe 2 NH][B(C 6 F 5 ) 4 ]、[HNMe(C 18 H 37 ) 2 ][B(C 6 F 5 ) 4 ]、B(C 6 F 5 ) 3 One or a mixture of several of them.
6. The method of claim 5, wherein the rare earth organometallic catalyst is prepared by the steps of: reacting a metallocene ligand with alkyl lithium in the solvent to obtain a ligand lithium salt, then adding the ligand lithium salt into anhydrous rare earth chloride for reaction, finally adding alkyl lithium or alkyl magnesium halide solution for reaction, and removing the solvent to obtain the rare earth organic metal catalyst.
7. The method for preparing a cyclic olefin copolymer according to claim 6, wherein: the anhydrous rare earth chloride is scandium trichloride, yttrium trichloride, lutetium trichloride, neodymium trichloride, holmium trichloride, samarium trichloride, gadolinium trichloride, ytterbium trichloride, europium trichloride or lanthanum trichloride.
8. The method for producing a cycloolefin copolymer according to claim 6, characterized in that: the metallocene ligand is selected from one of cyclopentadienyl, indenyl and fluorenyl ligands containing any substituent group.
9. The method for producing a cycloolefin copolymer according to claim 6, characterized in that: the solvent comprises tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydrothiophene, tetrahydropyran, tetramethylethylenediamine and 1, 2-dimethoxyethane.
10. The method for producing a cycloolefin copolymer according to claim 6, characterized in that: the alkyl lithium is selected from at least one of methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, N-butyl lithium, sec-butyl lithium, amyl lithium, hexyl lithium, cyclohexyl lithium, N-eicosyl lithium, phenyl lithium, naphthyl lithium, trimethylsilylmethylene lithium and N, N-dimethylbenzyl lithium; the alkyl magnesium halide is selected from at least one of methyl magnesium bromide, ethyl magnesium bromide, allyl magnesium bromide, cycloheptyl magnesium bromide, n-butyl magnesium bromide, ethyl magnesium chloride, isopropyl magnesium chloride and 2-methylbutyl magnesium chloride.
CN202211514298.9A 2022-11-30 2022-11-30 Preparation method of cycloolefin copolymer Pending CN115850548A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104098608A (en) * 2013-04-03 2014-10-15 中国石油化工股份有限公司 Scandium metallocene catalyst precursor, preparation method and application thereof, and preparation method for copolymer
CN108191999A (en) * 2018-01-02 2018-06-22 大连理工大学 A kind of preparation method of rare earth organo-metallic catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104098608A (en) * 2013-04-03 2014-10-15 中国石油化工股份有限公司 Scandium metallocene catalyst precursor, preparation method and application thereof, and preparation method for copolymer
CN108191999A (en) * 2018-01-02 2018-06-22 大连理工大学 A kind of preparation method of rare earth organo-metallic catalyst

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