CN112812211B - Polymerization method for efficiently regulating and controlling molecular weight of cycloolefin copolymer through reversible coordination chain transfer - Google Patents
Polymerization method for efficiently regulating and controlling molecular weight of cycloolefin copolymer through reversible coordination chain transfer Download PDFInfo
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Abstract
The invention discloses a polymerization method for efficiently regulating and controlling the molecular weight of a cycloolefin copolymer by reversible coordination chain transfer, which belongs to the technical field of polymer preparation and comprises the following steps: sequentially adding a cocatalyst, a hydrocarbon compound solvent, a metal alkyl compound chain transfer agent, a cycloolefin and a zirconocene metal catalyst into a reaction vessel, introducing ethylene gas, carrying out polymerization reaction for 2-10 min at 50-100 ℃, and adding ethanol to terminate polymerization after the polymerization is completed; pouring the reaction solution into a container containing a precipitator, and then filtering, washing and vacuum drying to obtain the cyclic olefin copolymer. A series of poly (ethylene-co-norbornene) copolymers are synthesized by utilizing coordination chain transfer, the molecular weight and the molecular weight distribution of the ethylene-norbornene copolymer (COC) are controllable, and a polymerization method with controllable activity characteristics is provided by utilizing a coordination chain transfer technology, so that the wide application of the coordination chain transfer technology in the synthesis of COC type materials is widened.
Description
Technical Field
The invention relates to the technical field of polymer preparation, in particular to a polymerization method for efficiently regulating and controlling the molecular weight of a cyclic olefin copolymer by reversible coordination chain transfer.
Background
Since the development and industrialization of polyolefins (PP, PE, etc.) by Ziegler-Natta utilizing olefin coordination polymerization, the development of olefin coordination polymerization has gradually matured. Coordination polymerization generally involves four motif reactions in a coordination-insertion mechanism: chain initiation, chain propagation, chain transfer and chain termination, wherein the chain transfer of coordination polymerization is very abundant, including beta hydrogen elimination, chain transfer to monomers, chain transfer reactions to cocatalyst metal alkyls and to hydrogen molecules, and the like. In the traditional olefin coordination polymerization, chain growth and chain transfer are in a competitive relationship, and the chain growth rate is far higher than the chain transfer rate, so that a single transition metal catalyst molecule can only grow a macromolecular chain, and the metal catalyst molecule which usually participates in polymerization can not participate in new polymerization reaction. In recent years, theThe difficulty that only one molecular chain can be generated by one active center during coordination polymerization is overcome, and reversible Coordination Chain Transfer Polymerization (CCTP) is developed by polymer scientists on the basis of the traditional olefin coordination polymerization. As shown in FIG. 1, by selecting a suitable transition metal catalyst in a reversible coordination chain transfer polymerization system and containing a large amount of an alkyl metal chain transfer agent, chain transfer to the alkyl metal will predominate in the chain transfer reaction, and this chain transfer reaction is rapidly reversible with respect to chain growth, i.e., the polymer chain is capable of rapid and reversible exchange between the metal catalyst and the chain transfer agent. In the reversible reaction process, the alkyl on the chain transfer agent and the central metal form a new active center to continue chain growth, the original active polymer chain is exchanged to the alkyl metal compound to form a dormant polymer chain, the newly generated polymer chain and the dormant polymer chain continuously carry out rapid chain exchange reaction, and each transition metal active center can be exchanged into a plurality of polymer chains, so that the chain length of each polymer chain is uniform, and the molecular weight distribution are controllable. This reversible rapid chain transfer (strand exchange) is the mechanism of CCTP in fig. 1. In addition, if the chain transfer rate is much greater than the chain growth rate (k)e>>kp) It appears that Chain Growth occurs on metal alkyl compounds of which the main group is a transition metal complex, and this is regarded as catalytic, which is also called Catalytic Chain Growth (CCG). CCTP is very similar to controllable living anionic polymerization, and on one hand, the CCTP has the advantages of controllable polymer molecular weight and molecular weight distribution, designability preparation of various block copolymers, functionalization modification of polymer chain ends and the like; on the other hand, it is worth noting that CCTP also has stereoselectivity for monomer optics compared to traditional anions, and each active center thereof can form multiple polymer chains, and the transition metal active center utilization can exceed 100%, achieving the recycling economy of the active metal center.
In a traditional coordination polymerization system, the chain growth rate is usually 3-4 orders of magnitude higher than the chain transfer rate, and therefore reversible coordination chain transfer polymerization can be realized only by selecting a proper catalytic system. Applications ofThe most widely studied is the catalytic system composed of aluminum alkyl as a chain transfer agent and a transition metal catalyst, and zinc alkyl, magnesium alkyl and the like can also be used as the chain transfer agent. The kind of so-called chain transfer agent can have a great influence on the polymer molecular weight and its distribution. Sita et al found that when propylene polymerization was catalyzed by a pincer-shaped amidino zirconocene catalyst, boron salts [ PhNMe ] were used2H][B(C6F5)4]The metal center is activated, and a rapid and reversible methyl transfer reaction exists between active species and dormant species in a polymerization system. When the amount of the activating agent is the same as that of the catalyst, the obtained polymer is isotactic polypropylene (iPP); when the amount of the activator is half of the amount of the catalyst, the polymerization product is atactic polypropylene (aPP), which is caused by the stereoisomerisation of the metal centre, and the addition of the activator is controlled to obtain the atactic-isotactic diblock polypropylene. Wei et al, polyethylene materials having a narrow Poisson distribution of molecular weights, which can be synthesized at lower ethylene pressures at 25 ℃ using an organometallic hafnium as a catalyst, a zinc alkyl as a chain transfer agent, and a borate compound as a co-catalyst.
The application of reversible coordination chain transfer in copolymerization is also a hot spot of recent comparative research, and random copolymers and block copolymers can be obtained according to different feeding modes. In 2009, Visseaux et al, using a hydroborated rare earth metal catalyst system in combination with alkyl magnesium as a chain transfer agent, were able to achieve reversible coordination chain transfer copolymerization of styrene/1-hexene and styrene/isoprene to prepare a random copolymer material with controllable molecular weight. The traditional copolymer prepared by coordination polymerization has the defects of uncontrollable molecular weight, wide molecular weight distribution, low utilization rate and poor tolerance of a catalyst, and is difficult to industrially produce, particularly cycloolefin copolymers, so that the wide application of cycloolefin materials is limited.
Disclosure of Invention
The invention mainly aims to provide a polymerization method for efficiently controlling the molecular weight and the molecular weight distribution of a Cyclic Olefin Copolymer (COC) by reversible coordination chain transfer. Aiming at the state of the prior art, the technical problem to be solved is to optimize the polymerization conditions, realize the controllability of the molecular weight of the COC copolymer and further widen the application of the coordination chain transfer polymerization method in the copolymerization of cycloolefins.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a polymerization method for efficiently regulating and controlling the molecular weight of a cyclic olefin copolymer by reversible coordination chain transfer, which comprises the following steps:
(1) sequentially adding a cocatalyst, a hydrocarbon compound solvent, a metal alkyl compound chain transfer agent, a cycloolefin and a zirconocene metal catalyst into a reaction vessel, introducing ethylene gas, wherein the ethylene pressure is 1-5 atm, preferably 1atm, carrying out polymerization reaction for 2-10 min at 50-100 ℃, adding ethanol to terminate polymerization after the polymerization is finished, preferably polymerizing for 2-10 min at 50 ℃;
(2) pouring the reaction liquid obtained in the step (1) into a container containing a precipitator, and then filtering, washing and vacuum drying to obtain the cyclic olefin copolymer.
Preferably, the hydrocarbon compound solvent includes at least one of benzene and its homologues (toluene, xylene, etc.), naphthalene and its homologues, alkane and its homologues, cycloalkane and its homologues. More preferably, the hydrocarbon compound is a toluene solvent. Preferably, the total volume of polymerization is 50 ml.
Preferably, the metal alkyl compound chain transfer agent comprises trimethylaluminum (AlMe)3) Triethylaluminium (AlEt)3) Triisopropylaluminum, triisobutylaluminum (Al)iBu3) Ethylaluminum dichloride, diethylaluminum chloride, diethylzinc (ZnEt)2) Diethyl magnesium, diisobutyl magnesium, n-butyl ethyl magnesium or n-butyl lithium. More preferably one of trimethylaluminum and diethylzinc.
Preferably, the cyclic olefin comprises one of norbornene, cyclopentene, dicyclopentadiene or monocyclopentadiene. Norbornene is more preferred.
Aiming at that the zirconocene metal catalyst has certain copolymerization capacity on ethylene and norbornene, the invention selects different chain transfer agents, such as triisobutyl aluminum (Al)iBu3) Triethylaluminium (AlEt)3) Trimethylaluminum (AlMe)3) Anddiethyl zinc (ZnEt)2) Etc. respectively researching the influence rule of the monomer on the chain transfer in the copolymerization of ethylene and norbornene, the schematic diagram of the chain transfer of the invention is shown in FIG. 2, and it can be seen from FIG. 2 that the chain transfer rate constant of the invention is far greater than the chain growth rate constant (k)ex>>kp). In addition, a series of synthesized polymers are characterized, and the thermodynamic behaviors of the polymers are researched by adopting high-temperature nuclear magnetic carbon spectrum to characterize the chemical structures of the polymers, high-temperature GPC to test the molecular weights and the distribution of the polymers, DSC and the like.
The invention uses zirconium metal catalyst and dry methylaluminoxane (dMAO) cocatalyst to form a catalytic system, combines different types of chain transfer agents, and synthesizes a series of ethylene/norbornene copolymers with controllable molecular mass by a coordination chain transfer method. Firstly, according to the fact that a zirconium metal catalyst has a certain degree of copolymerization capacity on ethylene and norbornene, the influence of polymerization time, different kinds of chain transfer agents and chain transfer agent matching ratios on coordination chain transfer polymerization is systematically researched, and the control on the molecular mass of an ethylene/norbornene copolymer is achieved. GPC results showed that the coordination chain transfer efficiency was the highest with diethyl zinc. Subsequently, reversible coordination chain transfer polymerization of various zirconium-based metal catalysts was systematically investigated in determining the ratio of diethylzinc relative to the catalyst. The comprehensive GPC results show that the coordination chain transfer efficiency is rapid and reversible by using a transfer agent such as diethyl zinc. In addition, the relative molecular mass of the ethylene/norbornene copolymer increases linearly with time, and the molecular weight distribution thereof changes in a narrow range, which is characteristic of living polymerization. Thus, the application of the coordination chain transfer polymerization method in the copolymerization of cycloolefins is widened.
Preferably, the cocatalyst is dry methylaluminoxane (dMAO).
Preferably, the zirconocene metal catalyst comprises: Rac-Et (Ind)2ZrCl2、Rac-Me2Si(Ind)2ZrCl2、Rac-Ph2Me(Cyc)(9-Ind)ZrCl2、Rac-Me2Si(2-Me-Ind)2ZrCl2、Rac-H2C(3-tert-BuInd)2ZrCl2The structural formula is as follows:
more preferably, the zirconocene metal catalyst is Cat.1(Rac-Et (Ind)2ZrCl2) And Cat.2 (Rac-Me)2Si(Ind)2ZrCl2) One kind of (1).
Preferably, the precipitant comprises at least one of ethanol, methanol, petroleum ether, diethyl ether, n-hexane, acetone, n-pentane, tetrahydrofuran, or dichloromethane. The precipitator is preferably a mixed solution of ethanol and hydrochloric acid with the mass fraction of 0.5%.
Preferably, the molar ratio of the metal alkyl compound chain transfer agent to the zirconocene metal catalyst is 5: 1-500: 1.
Preferably, the molar ratio of the cocatalyst to the zirconocene metal catalyst is 500: 1-3000: 1.
Preferably, the molar ratio of ethylene to cycloolefin is 5:1 to 1: 1.
The invention also provides a cycloolefin copolymer prepared by utilizing the polymerization method for efficiently regulating and controlling the molecular weight of the cycloolefin copolymer by utilizing reversible coordination chain transfer, wherein the weight average molecular weight of the cycloolefin copolymer is 1 x 104～25×104g/mol, PDI between 1.5 and 3, copolymerization activity of 1 to 20kgpolymer mmolCat. -1h-1In the meantime.
The invention discloses the following technical effects:
the invention synthesizes a series of poly (ethylene-co-norbornene) copolymers by utilizing coordination chain transfer, and aims at the disadvantage of the traditional coordination polymerization to realize the high efficiency and controllability of the molecular weight and the molecular weight distribution of the ethylene and norbornene copolymer (COC), and the insertion rate of the copolymer norbornene prepared by the invention is adjustable between 0.5 percent and 60 percent. The selection of different kinds of chain transfer agents suggests a polymerization process with controlled activity characteristics by the coordination chain transfer technique. The technology is not reported in many technical fields, so that the wide application of the coordination chain transfer technology in the synthesis of COC type materials is widened.
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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 to be used 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 inventive exercise.
FIG. 1 is a schematic diagram of a reversible coordination chain transfer polymerization mechanism mentioned in the background section;
FIG. 2 is a schematic illustration of the chain transfer of the present invention;
FIG. 3 is a graph of the molecular weight and molecular weight distribution over time of the copolymer obtained with catalyst Cat.1 in example 1 of the present invention;
FIG. 4 is a graph of the molecular weight and molecular weight distribution over time of the copolymer obtained with catalyst Cat.2 in example 2 of the present invention;
FIG. 5 is a gel permeation chromatogram of the copolymer in example 6 of the present invention;
FIG. 6 is a gel permeation chromatogram of the copolymer in 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. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between 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 process of synthesizing the catalyst, the operation is carried out in an MBraun glove box or under the protection of inert gases such as nitrogen or argon by using standard Schlenk technology by a person skilled in the art except for special instructions, and the solvent involved in the invention is an anhydrous and oxygen-free solvent after post-treatment. In addition, all moisture and oxygen sensitive manipulations during the preparation of the synthetic poly (ethylene-co-norbornene) copolymer are performed by those skilled in the art in a MBraun glove box or under nitrogen using standard Schlenk techniques.
The obtained copolymer was correlated, the chemical structure of the polymer was characterized by nuclear magnetic resonance spectroscopy (NMR), the thermal properties of the copolymer were characterized by Differential Scanning Calorimetry (DSC), and the molecular weight and molecular weight distribution of the copolymer were characterized by high temperature gel chromatography (GPC). In which the copolymer is1H and13c NMR was measured at 120 ℃ by a Bruker-400 NMR spectrometer using TMS as an internal standard and deuterated o-dichlorobenzene or deuterated 1,1,2, 2-tetrachloroethane as a solvent. Copolymer melting temperature (T)m) And glass transition temperature (T)g) By differenceAnd (3) measuring by a scanning calorimeter (Q2000 DSC), wherein the measuring condition is that the temperature rising/reducing rate is 20 ℃/min under the nitrogen atmosphere. Gel chromatography was performed by Gel Permeation Chromatography (GPC) PL GPC-220 type. The tester was RI-Laser, PL EasiCal PS-1 was used as a standard, the packed column was Plgel 10 μm MIXED-BLS, 1,2, 4-Trichlorobenzene (TCB) was used as a solvent (0.05 wt% of 2, 6-di-tert-butyl-4-methylphenol was added as an antioxidant), the test temperature was 150 ℃ and the flow rate was 1.0 mL/min.
The zirconocene metal catalyst is Cat.1-4 which is directly purchased from carbofuran company, and the Cat.5 is synthesized according to related domestic patents or documents (patent number: 201811164523.4 or Organometallics 2000,19(4),420 ACS database).
Example 1
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.1(Rac-Et (Ind)2ZrCl2) The catalyst carries out coordination chain transfer polymerization, and the reaction route is as follows:
the specific reaction steps are as follows: injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L norbornene toluene solution, 30 mu mol of diethyl zinc as a chain transfer agent, and then adding 3 mu mol of catalyst toluene solution to maintain the reaction system at 50ml, then rapidly introducing 1atm ethylene gas into the reaction system, and reacting for 2,4, 6, 8 and 10min under the action of violent stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. And finally, slowly pouring the reacted solution into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio is 50: 1) for sedimentation, and repeatedly filtering, washing and vacuum drying to obtain the ethylene/norbornene copolymer for subsequent characterization.
The results of nuclear magnetic resonance and DSC tests on the ethylene/norbornene copolymer obtained in the above manner are shown in FIG. 3, and the results of the tests show that the NBE insertion rate of the ethylene/norbornene copolymer obtained by coordination chain transfer polymerization in this example is 8-32%, and the NBE insertion rate is determined to be co-determined by the following co-polymerization methodGlass transition temperature (T) of the polymerg) The polymer has a melting point of 120-121 ℃, and a copolymerization activity of 1.2-5.6 kg, and the polymerization with a high partial insertion rate is amorphous behaviorpolymer mmolCat. -1h-1. High-temperature GPC analysis shows that the molecular weight is linearly increased along with the gradual increase of the reaction time, and the molecular weight distribution is maintained in a narrow range (PDI is 1.9-2.9), which indicates that the coordination chain transfer polymerization has the characteristics of living polymerization. In addition, data for specific copolymers are shown in table 1.
Example 2
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.2 (Rac-Me)2Si(Ind)2ZrCl2) The catalyst carries out coordination chain transfer polymerization, and the reaction route is as follows:
the specific reaction steps are as follows: injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L norbornene toluene solution, 30umol of diethyl zinc as a chain transfer agent and 3 mu mol of catalyst toluene solution, keeping the reaction system at 50ml, rapidly introducing 1atm ethylene gas into the reaction system, and reacting for 2,4, 6, 8 and 10min under the action of violent stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. And finally, slowly pouring the reacted solution into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio is 50: 1) for sedimentation, and repeatedly filtering, washing and vacuum drying to obtain the ethylene/norbornene copolymer for subsequent characterization.
The results of nuclear magnetic resonance and DSC analysis of the ethylene/norbornene copolymer obtained above are shown in FIG. 4, and the results of the test show that the NBE insertion rate of the ethylene/norbornene copolymer obtained by coordination chain transfer polymerization in this example is 5-40%, and the glass transition temperature (T) of the copolymer is 5-40%g) 25 to 125 ℃, a melting point of 120 to 136 ℃ and a copolymerization activity of 1.1 to 8.6kgpolymer mmolCat. -1h-1. . High-temperature GPC analysis shows that the molecular weight is linearly increased along with the gradual increase of the reaction time, and the molecular weight distribution is maintained in a narrow range (PDI is 2.3-2.7), which indicates that the coordination chain transfer polymerization has the characteristics of living polymerization. In addition, data for specific copolymers are shown in table 1.
Example 3
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.3 (Rac-Ph)2Me(Cyc)(9-Ind)ZrCl2) The catalyst carries out coordination chain transfer polymerization, and the reaction route is as follows:
the specific reaction steps are as follows: injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L norbornene toluene solution, 30umol of diethyl zinc as a chain transfer agent and 3 mu mol of catalyst toluene solution, keeping the reaction system at 50ml, rapidly introducing 1atm ethylene gas into the reaction system, and reacting for 2,4, 6, 8 and 10min under the action of violent stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. And finally, slowly pouring the reacted solution into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio is 50: 1) for sedimentation, and repeatedly filtering, washing and vacuum drying to obtain the ethylene/norbornene copolymer for subsequent characterization.
The results of nuclear magnetic resonance and DSC tests and analysis of the ethylene/norbornene copolymer obtained above indicated that the NBE insertion rate of the ethylene/norbornene copolymer obtained by coordination chain transfer polymerization in this example was 9-32%, and the glass transition temperature (T) of the copolymer wasg) 35 to 110 ℃, a melting point of 124 to 130 ℃, and a copolymerization activity of 0.2 to 5.1kgpolymermmolCat. -1h-1. . High temperature GPC analysis shows that the molecular weight increases linearly with increasing reaction time, and the molecular weight distribution is maintained in a narrow rangeThe change (PDI is 1.6-2.0) shows that the coordination chain transfer polymerization has the characteristic of living polymerization. In addition, data for specific copolymers are shown in table 1.
Example 4
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.4 (Rac-Me)2Si(2-Me-Ind)2ZrCl2) The catalyst carries out coordination chain transfer polymerization, and the reaction route is as follows:
the specific reaction steps are as follows: injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L norbornene toluene solution, 30umol of diethyl zinc as a chain transfer agent and 3 mu mol of catalyst toluene solution, keeping the reaction system at 50ml, rapidly introducing 1atm ethylene gas into the reaction system, and reacting for 2,4, 6, 8 and 10min under the action of violent stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. And finally, slowly pouring the reacted solution into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio is 50: 1) for sedimentation, and repeatedly filtering, washing and vacuum drying to obtain the ethylene/norbornene copolymer for subsequent characterization.
The results of nuclear magnetic resonance and DSC tests and analysis of the ethylene/norbornene copolymer obtained above indicated that the NBE insertion rate of the ethylene/norbornene copolymer obtained by coordination chain transfer polymerization in this example was 10-43%, and the glass transition temperature (T) of the copolymer was 10-43%g) 45-131 ℃, the melting point of 118-128 ℃, and the copolymerization activity of 1.1-5.7 kgpolymermmolCat. -1h-1. High-temperature GPC analysis shows that the molecular weight is linearly increased along with the gradual increase of the reaction time, and the molecular weight distribution is maintained in a narrow range (PDI is 1.9-2.5), which indicates that the coordination chain transfer polymerization has the characteristics of living polymerization. In addition, data for specific copolymers are shown in table 1.
Example 5
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.5 (Rac-H)2C(3-tert-BuInd)2ZrCl2) The catalyst carries out coordination chain transfer polymerization, and the reaction route is as follows:
the specific reaction steps are as follows: injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L norbornene toluene solution, 30umol of diethyl zinc as a chain transfer agent and 3 mu mol of catalyst toluene solution, keeping the reaction system at 50ml, rapidly introducing 1atm ethylene gas into the reaction system, and reacting for 2,4, 6, 8 and 10min under the action of violent stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. And finally, slowly pouring the reacted solution into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio is 50: 1) for sedimentation, and repeatedly filtering, washing and vacuum drying to obtain the ethylene/norbornene copolymer for subsequent characterization.
The results of nuclear magnetic resonance and DSC tests and analysis of the ethylene/norbornene copolymer obtained in the above-mentioned manner show that the NBE insertion rate of the ethylene/norbornene copolymer obtained by coordination chain transfer polymerization in this example is 0.2-1%, the copolymer has no glass transition temperature, the melting point is 136-138 ℃, and the copolymerization activity is 1.5-7.9 kgpolymer mmolCat. -1h-1. High-temperature GPC analysis shows that the molecular weight is linearly increased along with the gradual increase of the reaction time, and the molecular weight distribution is maintained in a narrow range (PDI is 2.1-2.7), which indicates that the coordination chain transfer polymerization has the characteristics of living polymerization. In addition, data for specific copolymers are shown in table 1.
Example 6
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.1(Rac-Et (Ind)2ZrCl2) Coordination chain transfer polymerization by catalystThe lines are as follows:
the specific reaction steps are as follows: injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L norbornene toluene solution, 0-20 eq (0, 5, 10 and 20 eq) of diethyl zinc chain transfer agent with different equivalents and adding 3 mu mol of catalyst toluene solution to maintain the reaction system at 50ml, then rapidly introducing 1atm of ethylene gas into the reaction system, and reacting for 3min under the action of vigorous stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. And finally, slowly pouring the reacted solution into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio is 50: 1) for sedimentation, and repeatedly filtering, washing and vacuum drying to obtain the ethylene/norbornene copolymer for subsequent characterization.
The results of nuclear magnetic resonance and DSC analysis of the ethylene/norbornene copolymer obtained above are shown in FIG. 5, and the results of the test show that the NBE insertion rate of the ethylene/norbornene copolymer obtained by coordination chain transfer polymerization in this example is 20-30%, and the glass transition temperature (T) of the copolymer isg) The temperature is 45-60 ℃, the melting point is avoided, and the polymerization shows an amorphous behavior. The copolymerization activity is 2.5-3.9 kgpolymer mmolCat. -1h-1. High-temperature GPC result analysis shows that the molecular weight of the copolymer is continuously reduced along with the increase of the equivalent weight of the diethyl zinc chain transfer agent in a Cat.1 system, the molecular weight distribution is maintained to be changed in a narrow range (PDI is 1.6-2.4), and the diethyl zinc chain transfer agent can make contribution of reversible rapid chain exchange in coordination chain transfer polymerization, and the chain transfer efficiency (Chains/Zr) is 4-18%.
Example 7
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.2 (Rac-Me)2Si(Ind)2ZrCl2) Coordination chain transfer polymerization by the catalyst. The reaction route is as follows:
the specific reaction steps are as follows: injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L norbornene toluene solution, 0-20 eq (0, 5, 10 and 20 eq) of diethyl zinc serving as a chain transfer agent and 3 mu mol of catalyst toluene solution to maintain the reaction system at 50ml, rapidly introducing 1atm ethylene gas into the reaction system, and reacting for 3min under the action of vigorous stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. And finally, slowly pouring the reacted solution into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio is 50: 1) for sedimentation, and repeatedly filtering, washing and vacuum drying to obtain the ethylene/norbornene copolymer for subsequent characterization.
The results of nuclear magnetic resonance and DSC analysis of the ethylene/norbornene copolymer obtained above are shown in FIG. 6, and the results of the test show that the NBE insertion rate of the ethylene/norbornene copolymer obtained by coordination chain transfer polymerization in this example is 25-35%, and the glass transition temperature (T) of the copolymer isg) The temperature is 55-70 ℃, and the melting point is avoided. The copolymerization activity is 8-24 kgpolymermmolCat. -1h-1. High-temperature GPC result analysis shows that the molecular weight of the copolymer is continuously reduced along with the increase of the equivalent weight of the diethyl zinc chain transfer agent in a Cat.2 system, the molecular weight distribution is maintained to be changed in a narrow range (PDI is 2.3-2.8), and the diethyl zinc chain transfer agent can make contribution of reversible rapid chain exchange in coordination chain transfer polymerization, and the chain transfer efficiency (Chains/Zr) is 4-18%.
Example 8
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.1(Rac-Et (Ind)2ZrCl2) Coordination chain transfer polymerization by the catalyst. The reaction route is as follows:
the specific reaction steps are as follows: injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L norbornene toluene solution, 100-400 eq of different equivalent of trimethylaluminum chain transfer agents and 3 mu mol of toluene solution of catalysts to maintain the reaction system at 50ml, rapidly introducing 1atm ethylene gas into the reaction system, and reacting for 3min under the action of vigorous stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. And finally, slowly pouring the reacted solution into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio is 50: 1) for sedimentation, and repeatedly filtering, washing and vacuum drying to obtain the ethylene/norbornene copolymer for subsequent characterization.
The results of nuclear magnetic resonance and DSC tests and analysis of the ethylene/norbornene copolymer obtained above indicated that the NBE insertion rate of the ethylene/norbornene copolymer obtained by coordination chain transfer polymerization in this example was 20-28%, and the glass transition temperature (T) of the copolymer was 20-28%g) The temperature is 48-60 ℃, the melting point is not existed, and the polymer shows amorphous behavior. The copolymerization activity is 4.1-8.2 kgpolymer mmolCat. -1h-1. High-temperature GPC result analysis shows that the molecular weight of the copolymer is continuously reduced along with the increase of the equivalent weight of the trimethylaluminum chain transfer agent in a Cat.1 system, the molecular weight distribution is maintained to be changed in a narrow range (PDI is 2.5-2.9), and the trimethylaluminum chain transfer agent makes contribution of reversible rapid chain exchange in coordination chain transfer polymerization, and the chain transfer efficiency (Chains/Zr) is 4-38%.
Example 9
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.2 (Rac-Me)2Si(Ind)2ZrCl2) The catalyst carries out coordination chain transfer polymerization, and the reaction route is as follows:
the method comprises the following specific steps: injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L of norbornene toluene solution, 100-400 eq of trimethylaluminum with different equivalents as chain transfer agents and 3 mu mol of toluene solution of catalysts to maintain the reaction system at 50ml, rapidly introducing 1atm of ethylene gas into the reaction system, and reacting for 3min under the action of violent stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. And finally, slowly pouring the reacted solution into a beaker containing 300mL of ethanol/hydrochloric acid (50: 1) for sedimentation, and repeatedly filtering, washing and vacuum drying to obtain the ethylene/norbornene copolymer for subsequent characterization.
The ethylene/norbornene copolymer obtained in the above example was subjected to nuclear magnetic resonance and DSC tests and analyzed, and the results of the tests showed that the NBE insertion rate of the ethylene/norbornene copolymer obtained by coordination chain transfer polymerization in this example was 25 to 35%, and the glass transition temperature (T) of the copolymer was 25 to 35%g) 50-65 ℃ without melting point. The copolymerization activity is 5.1-8.2 kgpolymer mmolCat. - 1h-1. High-temperature GPC result analysis shows that the molecular weight of the copolymer is continuously reduced along with the increase of the equivalent weight of the trimethylaluminum chain transfer agent in a Cat.2 system, the molecular weight distribution is maintained to be changed in a narrow range (PDI is 1.9-2.5), and the trimethylaluminum chain transfer agent can make a contribution to reversible and rapid chain exchange in coordination chain transfer polymerization, and the chain transfer efficiency (Chains/Zr) is 3-15%.
Example 10
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.1(Rac-Et (Ind)2ZrCl2) Coordination chain transfer polymerization by the catalyst.
Injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L of norbornene toluene solution, 100-400 eq of trimethylaluminum with different equivalents as chain transfer agents and 3 mu mol of toluene solution of catalysts to maintain the reaction system at 50ml, rapidly introducing 1atm of ethylene gas into the reaction system, and reacting for 3min under the action of violent stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. And finally, slowly pouring the reacted solution into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio is 50: 1) for sedimentation, and repeatedly filtering, washing and vacuum drying to obtain the ethylene/norbornene copolymer for subsequent characterization.
The results of nuclear magnetic resonance and DSC tests and analysis of the ethylene/norbornene copolymer obtained above show that the NBE insertion rate of the ethylene/norbornene copolymer obtained by triethyl aluminum coordination chain transfer polymerization in this example is 22-28%, and the glass transition temperature (T) of the copolymer isg) The temperature is 50-60 ℃, the melting point is not existed, and the polymer shows amorphous behavior. The copolymerization activity is 11.1-22.2 kgpolymer mmolCat. -1h-1. High-temperature GPC result analysis shows that the molecular weight of the copolymer is continuously reduced along with the increase of the equivalent weight of the triethylaluminum chain transfer agent in a Cat.1 system, the molecular weight distribution is maintained to be changed in a narrow range (PDI is 1.8-2.4), and the triethylaluminum chain transfer agent can make a contribution to reversible rapid chain exchange in coordination chain transfer polymerization, and the chain transfer efficiency (Chains/Zr) is 4-37%.
Example 11
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.2 (Rac-Me)2Si(Ind)2ZrCl2) Coordination chain transfer polymerization by the catalyst. The reaction route is as follows:
the specific reaction process is as follows: injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L of norbornene toluene solution, 100-400 eq of trimethylaluminum with different equivalents as chain transfer agents and 3 mu mol of toluene solution of catalysts to maintain the reaction system at 50ml, quickly introducing 1atm of ethylene gas into the reaction system, and reacting for 3min under the action of violent stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. Finally, the reacted solution is slowly poured into a beaker containing 300mL of ethanol/hydrochloric acid (50: 1) for sedimentation, and then the polymer obtained is repeatedly filtered, washed and dried in vacuum for subsequent characterization.
The nuclear magnetic resonance and DSC tests and analysis results of the obtained polymer show that the NBE insertion rate of the ethylene/norbornene copolymer obtained by coordination chain transfer polymerization in the example is 30-38%, and the glass transition temperature (T) of the copolymer isg) 80-95 ℃ without melting point. The copolymerization activity is 14.1-32.2 kgpolymer mmolCat. -1h-1. High-temperature GPC result analysis shows that the molecular weight of the copolymer is continuously reduced along with the increase of the equivalent weight of the triethylaluminum chain transfer agent in a Cat.2 system, the molecular weight distribution is maintained to be changed in a narrow range (PDI is 1.8-2.4), and the triethylaluminum chain transfer agent can make a contribution to reversible rapid chain exchange in coordination chain transfer polymerization, and the chain transfer efficiency (Chains/Zr) is 2-10%.
Example 12
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.1(Rac-Et (Ind)2ZrCl2) Coordination chain transfer polymerization by the catalyst. The reaction route is as follows:
the coordination chain transfer polymerization process in this example is as follows: injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L of norbornene toluene solution, 100-400 eq of trimethylaluminum with different equivalents as chain transfer agents and 3 mu mol of toluene solution of catalysts to maintain the reaction system at 50ml, quickly introducing 1atm of ethylene gas into the reaction system, and reacting for 3min under the action of violent stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. Finally, the reacted solution is slowly poured into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio is 50: 1) for sedimentation, and then the polymer obtained is repeatedly filtered, washed and dried in vacuum for subsequent characterization.
The polymer obtained in the above-mentioned example was subjected to nuclear magnetic resonance and DSC tests and analyzed, and the results of the tests showed that the NBE insertion rate of the ethylene/norbornene copolymer obtained by triethyl aluminum coordination chain transfer polymerization in this example was 22-28%, and the glass transition temperature (T) of the copolymer wasg) The temperature is 50-60 ℃, the melting point is not existed, and the polymer shows amorphous behavior. The copolymerization activity is 4.1-8.2 kgpolymer mmolCat. -1h-1. High-temperature GPC results show that the molecular weight of the copolymer is continuously reduced along with the increase of the equivalent weight of the triisobutylaluminum chain transfer agent in the Cat.1 system, the molecular weight distribution is kept in a narrow range (PDI is 2.6-3.1), and the triisobutylaluminum transfer agent can make a contribution of reversible and rapid chain exchange in coordination chain transfer polymerization, and the chain transfer efficiency (Chains/Zr) is 10-37%.
Example 13
A polymerization method for efficiently regulating and controlling the molecular weight of cyclic olefin copolymer by reversible coordination chain transfer adopts Cat.2 (Rac-Me)2Si(Ind)2ZrCl2) Coordination chain transfer polymerization by the catalyst. The reaction route is as follows:
the specific steps of coordination chain transfer polymerization in this example are as follows:
injecting 40ml of toluene solvent by using a Schlenk experimental device and keeping high vacuum, heating the temperature in the system to 50 ℃, stirring for 5min, sequentially adding 6mmol of dMAO, 0.2mol/L of norbornene toluene solution, 100-400 eq of trimethylaluminum with different equivalents as chain transfer agents and 3 mu mol of toluene solution of catalysts to maintain the reaction system at 50ml, quickly introducing 1atm of ethylene gas into the reaction system, and reacting for 3min under the action of violent stirring; after completion of the polymerization, the polymerization was terminated by injecting 0.2ml of ethanol. And finally, slowly pouring the reacted solution into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio is 50: 1) for sedimentation, and repeatedly filtering, washing and vacuum drying to obtain the ethylene/norbornene copolymer for subsequent characterization.
The ethylene/norbornene copolymer obtained in the above example was subjected to nuclear magnetic resonance and DSC tests and analyzed, and the results of the tests showed that the insertion rate of the ethylene/norbornene copolymer obtained by coordination chain transfer polymerization in this example was 25 to 32%, and the glass transition temperature (T) of the copolymer was 25 to 32%g) The temperature is 70-85 ℃, and the melting point is avoided. The copolymerization activity is 0.4-12.2 kgpolymer mmolCat. -1h-1. High temperature GPC analysis showed that the molecular weight of the copolymer continued to decrease and the molecular weight distribution remained in a narrow range (PDI of 1.6 to 2.1) as the equivalent weight of the triisobutylaluminum chain transfer agent increased in the Cat.2 system, indicating that the triisobutylaluminum chain transfer agent contributed to the reversible and slow chain exchange in this coordination chain transfer polymerization, and the chain transfer efficiency (Chains/Zr) was 3 to 15%.
TABLE 1
The invention discloses and provides a polymerization method for efficiently regulating and controlling the molecular weight of a cycloolefin copolymer by reversible coordination chain transfer, which widens the application field of the reversible coordination chain transfer in the preparation of high-performance COC materials and has very important practical significance.
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 (2)
1. A polymerization method for efficiently regulating and controlling the molecular weight of a cyclic olefin copolymer by reversible coordination chain transfer is characterized by comprising the following steps:
(1) sequentially adding a cocatalyst, a hydrocarbon compound solvent, a metal alkyl compound chain transfer agent, a cycloolefin and a zirconocene metal catalyst into a reaction vessel, introducing ethylene gas, carrying out polymerization reaction for 2-10 min at 50-100 ℃, and adding ethanol to terminate polymerization after the polymerization is completed;
(2) pouring the reaction liquid obtained in the step (1) into a container containing a precipitator, and then filtering, washing and vacuum drying to obtain a cyclic olefin copolymer;
the hydrocarbon compound solvent is at least one of benzene and homologues thereof, naphthalene and homologues thereof, alkane and homologues thereof or cycloalkane and homologues thereof;
the metal alkyl compound chain transfer agent is one of trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, ethylaluminum dichloride, diethylaluminum chloride, diethylzinc, diethylmagnesium, diisobutylgagnesium, n-butylethylmagnesium or n-butyllithium;
the cycloolefin is one of norbornene, cyclopentene, dicyclopentadiene or monocyclopentadiene;
the zirconium metallocene catalyst is as follows: Rac-Et (Ind)2ZrCl2、Rac-Me2Si(Ind)2ZrCl2、Rac-Ph2Me(Cyc)(9-Ind)ZrCl2、Rac-Me2Si(2-Me-Ind)2ZrCl2Or Rac-H2C(3-tert-BuInd)2ZrCl2One of (1);
the precipitant comprises at least one of ethanol, methanol, petroleum ether, diethyl ether, n-hexane, acetone, n-pentane, tetrahydrofuran or dichloromethane;
the molar ratio of the metal alkyl compound chain transfer agent to the zirconocene metal catalyst is 5: 1-500: 1;
the molar ratio of the cocatalyst to the zirconocene metal catalyst is 500: 1-3000: 1, and the molar ratio of the ethylene to the cycloolefin is 5: 1-1: 1.
2. The polymerization method for efficiently regulating and controlling the molecular weight of cycloolefin copolymer according to claim 1, wherein the cocatalyst is dry methylaluminoxane.
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