CN109467660B - Synthesis of poly (ethylene-r-norbornene/ethylene) multiblock copolymer using chain shuttling method - Google Patents
Synthesis of poly (ethylene-r-norbornene/ethylene) multiblock copolymer using chain shuttling method Download PDFInfo
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- Health & Medical Sciences (AREA)
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- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a method for synthesizing poly (ethylene-r-norbornene/ethylene) multi-block copolymer by using a chain shuttling method, which comprises the steps of preparing a mixed catalyst, adding a polymerization monomer, adjusting the polymerization temperature, adding a cocatalyst and a chain shuttling agent, adding a catalyst to perform chain shuttling polymerization, terminating polymerization reaction, precipitating polymer solution and drying. The poly (ethylene-r-norbornene/ethylene) multi-block copolymer is synthesized for the first time by selecting diethyl zinc as a chain shuttling agent, synthesizing an ethylene/norbornene random chain segment as a soft segment by using a Rac-ethyl bridged dichlorobiindane zirconium catalyst, and synthesizing a polyethylene chain segment as a hard segment by using a Rac-3-tert-butyl substituted methine bridged dichlorobiindane zirconium catalyst. The method and the substance are not reported in many technologies, and provide conditions for realizing wide application of the novel material.
Description
Technical Field
The invention relates to the technical field of preparation of poly (ethylene-r-norbornene/ethylene) multi-block copolymer synthesized by a chain shuttling method, in particular to a preparation method of a poly (ethylene-r-norbornene/ethylene) multi-block copolymer elastomer material synthesized by selecting two zirconocene metal catalysts which have larger selectivity difference on ethylene and norbornene comonomers and similar structures.
Background
Since the pioneering work of Ziegler in coordination polymerization of olefins, scientific research and industrial application of coordination polymerization of olefins have been vigorously developed. Polyolefins synthesized by coordination polymerization have become the most widely used polymeric material with the highest production in the world. Because the polyolefin has small relative density, good chemical resistance and water resistance; good mechanical strength, electrical insulation and the like, and can be used for films, pipes, plates, various molded products, wires and cables and the like in production and life. It has wide application in agriculture, package, electronics, electric, automobile, machinery, daily sundries, etc. China is a high-consumption country of polyolefin materials, the traditional polyolefin materials can be produced by themselves and basically can be self-sufficient, but most of high-performance polyolefin materials depend on imports. In order to solve this dilemma, new polymerization methods and polymerization processes need to be explored, so that the performance and cost performance of polyolefin materials are continuously improved.
Chain shuttling polymerization is a new coordination polymerization method developed in the last decade, and can efficiently prepare polyolefin multi-block copolymers. Compared with other polymerization methods, the method has many advantages in the aspect of preparing the block copolymer, such as higher utilization efficiency of the catalyst, easier control of the copolymer structure, easier realization of large-scale application and the like. Chain shuttling polymerization is an extension of the concept of (reversible) coordinative chain transfer. Under copolymerization conditions, when the polyolefin chain with activity exists in a chain transfer agent and two different catalysts, comonomers participating in polymerization have different reactivity for different catalysts, and different monomers can form different sequence distributions on a polymer chain under the action of the chain transfer agent, so that a block polyolefin polymer with a certain distribution is prepared.
Arriola D J Et al, 2006, from Dow Chemical company, proposed the concept of chain shuttling in the Science journal, discovered by high throughput screening techniques that a hafnium dimethylpyridine amine catalyst with strong comonomer insertion capacity, and a zirconium bisphenoloxyamine FI catalyst with weak comonomer insertion capacity, in diethyl zinc (Et)2Zn) as chain shuttling agent, and a multi-block copolymer with a crystalline high-density polyethylene chain segment as a hard segment and an amorphous ethylene/octene random copolymer chain segment as a soft segment alternately is prepared.
It can be seen from the mechanism of polymerization that conditions and severity that need to be met to obtain efficient chain shuttling polymerization: the two catalysts do not interact with each other in the presence of the catalyst, have larger difference on the selectivity of monomers and similar catalytic activity, the chain shuttling agent and the two catalysts need to be matched simultaneously, the chain transfer rate is obviously smaller than the chain growth rate and higher than the chain termination rate, and the reversible coordination chain transfer efficiency is high, the activity of the main catalyst is high and the thermal stability is good. Still, James c. stevens can prepare isotactic stereoblock polypropylene by the self-generation of chiral isomers of the catalyst, using a racemic catalyst of organohafnium and trimethylaluminum in MAO as a chain transfer agent, and the growing polypropylene active chain is converted and grown on different chiral centers by using the chain transfer agent as a medium, thereby producing polypropylene multi-block polymers with different stereoconfigurations. In 2009, by using organic nickel and organic zirconium as catalysts, MAO as a cocatalyst and diethyl zinc as a chain shuttling agent, linear-hyperbranched segmented polyethylene can be prepared by converting and growing ethylene active chains on catalytic active centers of the organic nickel and the organic zirconium. Pan et al successfully synthesized hard-soft multi-block co-sPS-cis-1, 4-PIP (PBD) sPS-3,4-PIP (1,2-PBD), a multi-block copolymer sPS-cis-1,4-PIP-cis-1,4-PBD sPS-3,4-PIP-1,2-PBD consisting of three homopolymer segments by using different scandium metal catalysts and triisobutylaluminum as a chain shuttling agent. In 2014, French scientists Zinck further developed a rare earth catalytic chain shuttling copolymerization reaction, and synthesized a novel thermoplastic elastomer PS-tran-1,4-PIP multi-block copolymer by using half-sandwich lanthanum compound-high activity catalytic isoprene polymerization and ansa-sandwich neodymium compound-high activity catalytic styrene polymerization in the presence of two catalysts, and taking alkyl magnesium as a chain transfer agent and taking styrene and isoprene as monomers.
To date, the concept of chain shuttling copolymerization has been proposed for over a decade, and most successful chain shuttling has mainly focused on metals in the fourth subgroup, with the selectivity of the catalyst to the monomer being different, and the use of diethyl zinc as a chain shuttling agent to catalyze the copolymerization of ethylene and alpha-olefins to form soft and hard multi-block copolymers, thermoplastic elastomers. A series of successful chain shuttling examples of rare earth metal catalysts of subgroup III have also been reported, and the resulting polymers are difficult to produce industrially due to their poor performance and poor catalyst tolerance. The major problem at present is the small variety of products of polymers prepared by chain shuttling. Currently, there are only two examples for industrialization-different brands of ethylene and α -olefin multi-block copolymers reported by Dow Chemical company and PS-tran-1,4-PIP multi-block copolymers reported by Zinck. The selection of a proper catalytic system and monomers for chain shuttling polymerization to synthesize a novel polymer material is a major challenge in the field at present, such as copolymerization of ethylene and cycloolefin, ethylene and polar monomers and the like to prepare a novel soft and hard segmented copolymer. Due to the particularities of the microstructure, it shows a significant difference in macroscopic properties such as thermal properties, mechanical properties, crystallinity, etc., compared to conventional homopolymer, diblock or triblock polymers.
Disclosure of Invention
The technical problem to be solved by the invention is to solve the state of the prior art; the invention firstly researches the reversible coordination chain transfer of the ethylene and norbornene comonomers by selecting two catalysts with larger selectivity difference and similar structures, combining a cocatalyst and a chain transfer agent under proper polymerization conditions. In a polymerization system, two catalysts are combined with a cocatalyst and a chain transfer agent to carry out chain shuttling polymerization, so that a soft/hard segmented copolymer taking random ethylene-norbornene as a soft segment and crystalline ethylene segment as a hard segment is synthesized.
The technical scheme of the invention is as follows:
synthesizing a poly (ethylene-r-norbornene/ethylene) multi-block copolymer by using a chain shuttling method; the method is characterized by comprising the following steps:
(1) preparing a mixed catalyst: weighing a mixed catalyst of Rac-ethyl bridged dichlorobiindane zirconium and Rac-3-tert-butyl substituted methylene bridged dichlorobiindane zirconium, wherein the molar ratio of the mixed catalyst is 3: 1-1: 3, and dissolving the mixed catalyst in a polymerization solvent for later use;
(2) addition of polymerization monomers and adjustment of polymerization temperature: adding a comonomer of norbornene dissolved in a polymerization solvent to a polymerization reactor; introducing ethylene, wherein the ethylene pressure is 1-6 atm; adjusting the temperature of a polymerization reactor to 50-100 ℃;
(3) addition of cocatalyst and chain shuttling agent: adding dry methylaluminoxane dissolved in a polymerization solvent as a cocatalyst into a polymerization reactor; then adding diethyl zinc dissolved in a polymerization solvent into a polymerization reactor as a chain shuttling agent, and stirring for 3-5 min; keeping the temperature of the polymerization reactor at 50-100 ℃;
(4) and adding a catalyst to carry out chain shuttling polymerization: continuously keeping the temperature of the polymerization reactor at 50-100 ℃, adding the mixed catalyst solution prepared in the step (1) into a polymerization container, and polymerizing for 6-15 min;
the volume ratio of the polymerization solvent to the polymerization reactor is 1/3-2/3, the molar quantity of the norbornene is 0.2-5 mol/L relative to the volume of the polymerization solvent in the polymerization reactor, and the molar ratio of the cocatalyst to the mixed catalyst is 1000-2000: 1, the molar ratio of the chain shuttling agent to the mixed catalyst is 5-40;
(5) termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time in the step (4), opening the polymerization reactor and adding a quenching agent to quench the polymerization reaction;
(6) polymer solution precipitation and drying: and pouring the polymer solution into a precipitator, stirring, precipitating, filtering, and drying in a vacuum drying oven at 60-80 ℃ for 6-8 hours to obtain the polyolefin multi-block copolymer.
The polymerization solvent is toluene, benzene, xylene or cyclohexane; the preferred polymerization solvent is toluene.
Preferably, when the ethylene pressure is 1atm, the polymerization temperature in the step (2) is 50-70 ℃, and the polymerization temperature is continuously maintained in the steps (3) and (4);
preferably, when the ethylene pressure is 2-6 atm, the polymerization temperature in the step (2) is 80-100 ℃, and the polymerization temperature in the steps (3) and (4) is continuously maintained;
preferably, the molar quantity of the norbornene is 0.2-3 mol/L relative to the volume of a polymerization solvent in a polymerization reactor;
preferably, the molar ratio of the cocatalyst to the catalyst is 2000: 1;
preferably, the total polymerization solvent is 1/2 which is the volume ratio of the polymerization reactor;
preferably, the quenching agent and the precipitating agent used for the polymerization are both mixed solution of ethanol and hydrochloric acid; the mixing ratio is preferably 50/1.
The advantages and effects of the invention are illustrated as follows:
(1) the invention screens out two catalysts with similar structure and different monomer selectivity by reading documents and experiments, namely Rac-ethyl bridged dichlorobiindane zirconium (commercialized) and Rac-3-tert-butyl substituted methylene bridged dichlorobiindane zirconium (synthesized according to documents);
(2) by selecting diethyl zinc as a chain shuttling agent and utilizing a chain shuttling method proposed by Dow Chemical company, an ethylene/norbornene random chain segment is synthesized to be a soft segment by using a Rac-ethyl bridged dichlorobiindane zirconium catalyst, a polyethylene chain segment is synthesized to be a hard segment by using a Rac-3-tert-butyl substituted methylene bridged dichlorobiindane zirconium catalyst, and a poly (ethylene-r-norbornene/ethylene) multi-block copolymer is synthesized for the first time.
(3) The poly (ethylene-r-norbornene/ethylene) multiblock copolymer obtained by polymerization was confirmed by the characterization of the polymer, such as the study of the primary structure of the polymer by high temperature carbon spectrum, the study of the molecular weight and its distribution of the polymer by high temperature GPC, DSC and DMA, etc. We find that the polymer has a high melting point of 125-129 ℃, a low glass transition temperature of 35-80 ℃, is adjustable in a certain range according to the insertion rate of a comonomer, and shows good elastomer characteristics.
The invention utilizes chain shuttling technology to synthesize poly (ethylene-r-norbornene/ethylene) multi-block copolymer and develop high-performance polyolefin block copolymer material. Two catalysts with different monomer selectivity are selected, a polymer with unimodal distribution is obtained by a chain shuttling polymerization technology, and the elastomer material with excellent performance is obtained by adjusting the content of soft segments and hard segments. The method is not reported in many technologies, and provides conditions for realizing wide application of the novel material.
Drawings
FIG. 1 is a GPC curve of a polymer obtained in example 1 of the present invention;
FIG. 2 is a GPC chart of a polymer in polymerization of example 2 of the present invention;
FIG. 3 is a GPC chart of the polymer in example 6 of the present invention;
FIG. 4 is a DSC of the polymer of example 5 of the present invention.
Detailed Description
For a further understanding of the invention, the following description of the embodiments of the invention, taken in conjunction with the description of the embodiments and the accompanying drawings, is provided for the purpose of further illustrating the features and advantages of the invention, and is not intended to limit the scope of the claims.
The operations involved in the synthesis of the catalyst are carried out by those skilled in the art, except for the specific details, in an MBraun glove box or under nitrogen protection using standard Schlenk techniques, and the solvents involved in the present invention are anhydrous and oxygen-free solvents.
In the preparation of the synthetic poly (ethylene-r-norbornene/ethylene) multiblock copolymers, all moisture and oxygen sensitive manipulations were performed by one skilled in the art in a MBraun glove box or under nitrogen using standard Schlenk techniques.
The obtained polymer is subjected to related tests, the microstructure of the polymer is measured by adopting nuclear magnetic resonance spectroscopy, the melting temperature of the polymer is measured by adopting a differential thermal analysis method, and the molecular weight distribution index of the polymer are measured by adopting high-temperature gel chromatography. In which the polymer 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. The polymer melting temperature was measured by differential scanning calorimetry (Q2000 DSC) at a ramp-up/ramp-down rate of 20 deg.C/min in a nitrogen atmosphere. Gel chromatography was performed by using PL GPC-220 type gel permeation chromatograph. The tester was RI-Laser, the packed column was Plgel 10 μm MIXED-BLS, 1,2, 4-Trichlorobenzene (TCB) as solvent (0.05 wt% of 2, 6-di-tert-butyl-4-methylphenol was added as antioxidant) the test temperature was 150 ℃ and the flow rate was 150 ℃1.0mL/min, using PL EasiCal PS-1 as standard.
Two catalysts selected in the present invention, catalyst a was purchased from carbofuran and catalyst B was synthesized according to the related literature (Organometallics 2000,19(4),420 american chemical society ACS database).
Synthesis of tert-butyl substituted indene 80g of KOH were first added to 80mL of distilled water to prepare a KOH/water solution, and to a three-necked flask, an aqueous potassium hydroxide solution, 39mmol of indene, 3mL of methyltri-zinc ammonium chloride and 117mmol of tert-butyl bromide were sequentially added at room temperature with a stirring speed of 800rpm, and when the organic phase changed from colorless to green, the mixture was heated to 80 ℃ and refluxed for 2 days with condensed water. After cooling to room temperature, 80mL of diethyl ether was added for dilution, 2mol/L of HCl was added for neutralization of the alkaline system, followed by extraction and separation with a 500mL separating funnel, drying of the organic layer with anhydrous magnesium sulfate for 20 minutes, filtration, and purification of the product after the solvent was drained with a vacuum pump. The extract was dried over magnesium sulfate, filtered, and distilled at 140 ℃ under reduced pressure to give a pale yellow liquid with a yield of 40%.
Synthesis of t-butyl-substituted methylene-bridged bis-indene 92mmol of t-butyl potassium alcoholate (t-BuOK) and 480mmol of t-butyl-substituted indene dissolved in Dimethylformamide (DMF) were added in this order to a three-necked flask, then 230mmol of aqueous formaldehyde solution were added dropwise via a constant pressure dropping funnel, the mixture was stirred to mix the solution sufficiently and react, and the temperature was kept constant at about 25 ℃ with a water bath. After complete mixing for 30 minutes, bubbles were formed, which indicated that an exothermic reaction had occurred and the solution had changed from colorless to red and finally to deep red. Stirring was continued for 2 hours and the reaction was quenched rapidly by adding an ammonium chloride/ice water mixture to the reaction system via syringe. Purifying the product by diethyl ether extraction, reduced pressure rotary evaporation to remove solvent, recrystallization, etc., to obtain oily orange-red product with yield of 66%1H NMR(400MHz,CDCl3):δ7.70–7.09(m,8H,Ar),6.22(s,2H,＝CH),3.75(s,2H,CH),3.23(s,2H,CH2bridge),0.99(s,18H,t-Bu)。
Synthesis of tert-butyl-substituted methylene-bridged bis-chlorobiindane in a stream of dry nitrogen, 9.6mmol of tert-butyl-substituted methylene-bridged bis-indene are dissolved in 60mL of diethyl ether, the solution is introduced into a three-necked flask by syringe and the temperature of the solution is maintained at 0 ℃; 22mmol of n-butyllithium (n-BuLi) dissolved in hexane were then added dropwise to the three-necked flask via a constant pressure dropping funnel, with stirring once, and the temperature was raised to room temperature, and stirring was continued for 24h to give an orange-red suspension. 10.6mmol of zirconium tetrachloride (ZrCl)4) Dissolving in 60mL of toluene solution to form a suspension, carrying out the next experiment in a low-temperature tank, setting the temperature of the low-temperature tank to be-20 ℃, quickly mixing the two suspensions, adding the two suspensions into a round-bottom flask, immediately changing the suspension from orange to red, continuing to keep the temperature at-20 ℃ for 25min, heating to about-17 ℃ for 20min, then heating to 0 ℃ again for 20min, taking out the three-neck flask from the low-temperature tank, returning to the room temperature, and standing overnight. Filtering, distilling under reduced pressure, and vacuum filtering to obtain the final product, namely, the red powdery product, namely, tert-butyl substituted methylene bridged bis (chloroindene) zirconium. The product was recrystallized and washed rapidly with tetrahydrofuran to give a final product with a yield of 45%.1H NMR(400MHz,CD2Cl2):δ7.65(d,J＝8.9Hz,2H,Ar-H),7.40(d,J＝8.7Hz,2H,Ar-H),7.25–7.18(m,2H,Ar-H),7.02–6.94(m,2H,Ar-H),5.67(s,2H,Cp-H),4.68(s,2H,CH2bridge),1.26(s,18H,t-Bu)。
Example 1
This example shows that at a polymerization temperature of 50 ℃ and an ethylene pressure of 1atm, the molar content of diethyl zinc is 10 times that of the mixed catalyst, and the molar ratio of the mixed catalyst Rac-ethyl bridged dichlorobiindanium a to Rac-3-tert-butyl substituted methine bridged dichlorobiindanium B is 3: chain shuttling polymerization with a polymerization time of 6min under the condition of 1.
The chain shuttling polymerization of this example included the following steps:
(1) weighing and preparing a chain shuttling catalyst: weighing Rac-ethyl bridged dichlorobiindane zirconium and Rac-3-tert-butyl substituted methylene bridged dichlorobiindane zirconium mixed catalyst in a molar ratio of 3:1 in a glove box by using an analytical balance, fully dissolving in toluene, and leaving behind for later use.
(2) Addition of polymerization monomers and adjustment of polymerization temperature: adding a comonomer norbornene dissolved in toluene to a polymerization reactor; introducing ethylene, wherein the ethylene pressure is 1 atm; adding toluene to flush the residual comonomer at the feeding port and leading the residual comonomer to be completely filled into the polymerization reactor; the polymerization reactor temperature was adjusted to 50 ℃.
(3) Addition of cocatalyst and chain shuttling agent: adding dry methylaluminoxane dissolved in toluene as a cocatalyst into a polymerization reactor; then adding diethyl zinc dissolved in toluene into a polymerization reactor as a chain shuttling agent, and stirring for 3-5 min; maintaining the polymerization reactor temperature at 50 ℃;
(4) and adding a catalyst to carry out chain shuttling polymerization: keeping the temperature of the polymerization reactor at 50 ℃, quantitatively extracting the mixed catalyst prepared in the step (1) by using an injector, adding the mixed catalyst into a polymerization container, adding toluene, flushing the residual mixed catalyst at a feeding port to ensure that the mixed catalyst is completely put into the polymerization reactor, and carrying out polymerization reaction for 6 min;
wherein: the volume ratio of the toluene to the polymerization reactor was 0.5, the molar amount of norbornene relative to the volume of toluene in the polymerization reactor was 0.2mol/L, and the molar ratio of cocatalyst to mixed catalyst was 2000: 1, the molar ratio of the chain shuttling agent diethyl zinc to the mixed catalyst is 10;
(5) termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time of 6min, opening the polymerization reactor, adding 50/1 ethanol/hydrochloric acid, and quenching the polymerization reaction;
(6) polymer solution precipitation and drying: pouring the polymer solution into a solvent, wherein the volume ratio of ethanol to hydrochloric acid is 50; 1, stirring, precipitating, filtering by a Buchner funnel, and drying for 6-8 hours in a vacuum drying oven at 60-80 ℃ to obtain the constant-weight polyolefin multi-block copolymer.
High temperature GPC analysis of the resulting polymerization showed that, as shown in FIG. 1 of the accompanying drawing, RT (min) is the time of flow-out, the left axis is dw/dlogw, the molecular weight distribution is a symmetrical monomodal distribution, the molecular weight distribution varies over a narrow range, and the DSC and related physical property studies showed that chain shuttling polymerization was achieved under these conditions to give poly (ethylene-r-norbornene/ethylene) multiblock copolymers.
Example 2
This example shows that at a polymerization temperature of 50 ℃ and an ethylene pressure of 1atm, the molar content of diethyl zinc is 10 times that of the mixed catalyst, and the molar ratio of the mixed catalyst Rac-ethyl bridged dichlorobiindanium a to Rac-3-tert-butyl substituted methine bridged dichlorobiindanium B is 3: chain shuttling polymerization with a polymerization time of 15min under the condition of 1.
The chain shuttling polymerization of this example included the following steps:
(1) weighing and preparing a chain shuttling catalyst: weighing Rac-ethyl bridged dichlorobiindane zirconium and Rac-3-tert-butyl substituted methylene bridged dichlorobiindane zirconium mixed catalyst in a molar ratio of 3:1 in a glove box by using an analytical balance, fully dissolving in toluene, and leaving behind for later use.
(2) Addition of polymerization monomers and adjustment of polymerization temperature: adding a comonomer of norbornene dissolved in a polymerization solvent to a polymerization reactor; introducing ethylene, wherein the ethylene pressure is 1 atm; adding dimethylbenzene to flush residual comonomer at the feeding port, so that all the comonomer is fed into the polymerization reactor; the polymerization reactor temperature was adjusted to 50 ℃.
(3) Addition of cocatalyst and chain shuttling agent: adding dry methylaluminoxane dissolved in dimethylbenzene as a cocatalyst into a polymerization reactor; then adding diethyl zinc dissolved in xylene into a polymerization reactor as a chain shuttling agent, and stirring for 3-5 min; the temperature of the polymerization reactor was kept at 50 deg.C
(4) And adding a catalyst to carry out chain shuttling polymerization: keeping the temperature of the polymerization reactor at 50 ℃, quantitatively pumping the mixed catalyst prepared in the step (1) into a polymerization container by using an injector, adding dimethylbenzene, and flushing the residual mixed catalyst at a feeding port to ensure that the mixed catalyst is completely filled into the polymerization reactor, wherein the polymerization reaction time is 15 min. The volume ratio of the xylene to the polymerization reactor is 0.5, the molar quantity of the norbornene is 0.2mol/L relative to the volume of the xylene in the polymerization reactor, and the molar ratio of the cocatalyst to the mixed catalyst is 2000: 1, the molar ratio of the chain shuttling agent to the mixed catalyst is 10.
(5) Termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time of 15min, opening the polymerization reactor, adding 50/1 ethanol/hydrochloric acid, and quenching the polymerization reaction;
(6) polymer solution precipitation and drying: and pouring the polymer solution into an ethanol/hydrochloric acid 50/1 solvent, stirring, precipitating, filtering by a Buchner funnel, and drying for 6-8 hours at 60-80 ℃ in a vacuum drying oven to obtain the constant-weight polyolefin multi-block copolymer.
High temperature GPC analysis of the resulting polymerization showed that as shown in FIG. 2 of the drawing, RT (min) is the time of flow-out, the left axis is dw/dlogw, the molecular weight distribution is a symmetrical monomodal distribution, the molecular weight distribution varies within a narrow range, and the study of DSC and related physical properties showed that chain shuttling polymerization was achieved under these conditions to give poly (ethylene-r-norbornene/ethylene) multiblock copolymers.
Example 3
This example shows that at a polymerization temperature of 70 ℃ and an ethylene pressure of 1atm, the molar content of diethyl zinc is 15 times that of the mixed catalyst, and the molar ratio of the mixed catalyst Rac-ethyl bridged dichlorobiindanium a to Rac-3-tert-butyl substituted methine bridged dichlorobiindanium B is 1: chain shuttling polymerization with a polymerization time of 10min under the condition of 1.
The chain shuttling polymerization of this example included the following steps:
(1) weighing and preparing a chain shuttling catalyst: weighing Rac-ethyl bridged dichlorobiindane zirconium and Rac-3-tert-butyl substituted methylene bridged dichlorobiindane zirconium mixed catalyst in a molar ratio of 1:1 in a glove box by using an analytical balance, fully dissolving in toluene, and leaving behind for later use.
(2) Addition of polymerization monomers and adjustment of polymerization temperature: adding a comonomer norbornene dissolved in toluene to a polymerization reactor; introducing ethylene, wherein the ethylene pressure is 1 atm; adding toluene to flush the residual comonomer at the feeding port and leading the residual comonomer to be completely filled into the polymerization reactor; the polymerization reactor temperature was adjusted to 70 ℃.
(3) Addition of cocatalyst and chain shuttling agent: adding dry methylaluminoxane dissolved in toluene as a cocatalyst into a polymerization reactor; then adding diethyl zinc dissolved in toluene into a polymerization reactor as a chain shuttling agent, and stirring for 3-5 min; the temperature of the polymerization reactor was kept at 70 deg.C
(4) And adding a catalyst to carry out chain shuttling polymerization: keeping the temperature of the polymerization reactor at 50 ℃, quantitatively pumping the mixed catalyst prepared in the step (1) into a polymerization container by using an injector, adding toluene, flushing the residual mixed catalyst at a feeding port to ensure that the mixed catalyst is completely filled into the polymerization reactor, and carrying out polymerization reaction for 10 min. The volume ratio of the toluene to the polymerization reactor was 0.5, the molar amount of norbornene relative to the volume of toluene in the polymerization reactor was 0.2mol/L, and the molar ratio of cocatalyst to mixed catalyst was 2000: 1, the molar ratio of the chain shuttling agent to the mixed catalyst is 15.
(5) Termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time of 10min, opening the polymerization reactor, adding 50/1 ethanol/hydrochloric acid, and quenching the polymerization reaction;
(6) polymer solution precipitation and drying: pouring the polymer solution into a solvent, wherein the volume ratio of ethanol to hydrochloric acid is 50; 1, stirring, precipitating, filtering by a Buchner funnel, and drying for 6-8 hours in a vacuum drying oven at 60-80 ℃ to obtain the constant-weight polyolefin multi-block copolymer.
High temperature GPC analysis of the resulting polymerization showed that the molecular weight distribution was a symmetrical monomodal distribution, with the molecular weight distribution varying over a narrow range, and DSC and related physical property studies indicated that chain shuttling polymerization was achieved under these conditions to give poly (ethylene-r-norbornene/ethylene) multi-block copolymers.
Example 4
This example shows that at a polymerization temperature of 80 ℃ and an ethylene pressure of 4atm, the molar content of diethyl zinc is 5 times that of the mixed catalyst, and the molar ratio of the mixed catalyst Rac-ethyl bridged dichlorobiindanium a to Rac-3-tert-butyl substituted methine bridged dichlorobiindanium B is 1: chain shuttling polymerization with a polymerization time of 10min under the condition of 1.
The chain shuttling polymerization of this example included the following steps:
(1) weighing and preparing a chain shuttling catalyst: weighing a mixed catalyst of Rac-ethyl bridged dichlorobiindane zirconium and Rac-3-tert-butyl substituted methylene bridged dichlorobiindane zirconium in a molar ratio of 1:1 by using an analytical balance in a glove box, fully dissolving the mixed catalyst in cyclohexane, and keeping the mixed catalyst for later use.
(2) Addition of polymerization monomers and adjustment of polymerization temperature: adding a comonomer norbornene dissolved in toluene to a polymerization reactor; introducing ethylene, wherein the ethylene pressure is 4 atm; adding cyclohexane to flush the residual comonomer at the feeding port and leading the residual comonomer to be completely filled into the polymerization reactor; the polymerization reactor temperature was adjusted to 80 ℃.
(3) Addition of cocatalyst and chain shuttling agent: adding dry methylaluminoxane dissolved in cyclohexane as a cocatalyst into a polymerization reactor; then adding diethyl zinc dissolved in cyclohexane into a polymerization reactor as a chain shuttling agent, and stirring for 3-5 min; the temperature of the polymerization reactor is kept at 80 DEG C
(5) And adding a catalyst to carry out chain shuttling polymerization: keeping the temperature of the polymerization reactor at 80 ℃, quantitatively pumping the mixed catalyst prepared in the step (1) into a polymerization container by using an injector, adding cyclohexane, flushing the residual mixed catalyst at a feeding port to ensure that the mixed catalyst is completely put into the polymerization reactor, and carrying out polymerization reaction for 10 min. The volume ratio of the cyclohexane to the polymerization reactor was 0.5, the molar amount of norbornene was 1mol/L relative to the volume of cyclohexane in the polymerization reactor, and the molar ratio of cocatalyst to mixed catalyst was 2000: 1, the molar ratio of the chain shuttling agent to the mixed catalyst is 5.
(5) Termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time of 10min, opening the polymerization reactor, adding 50/1 ethanol/hydrochloric acid, and quenching the polymerization reaction;
(6) polymer solution precipitation and drying: and pouring the polymer solution into a solvent with the volume ratio of ethanol to hydrochloric acid being 50/1, stirring, precipitating, filtering by a Buchner funnel, drying for 6-8 hours at the temperature of 60-80 ℃ in a vacuum drying oven, and obtaining the constant-weight polyolefin multi-block copolymer.
High temperature GPC analysis of the resulting polymerization showed that the molecular weight distribution was a symmetrical monomodal distribution, with the molecular weight distribution varying over a narrow range, and DSC and related physical property studies indicated that chain shuttling polymerization was achieved under these conditions to give poly (ethylene-r-norbornene/ethylene) multi-block copolymers.
Example 5
This example shows that at a polymerization temperature of 100 ℃ and an ethylene pressure of 4atm, the content of diethyl zinc is 10 times that of the mixed catalyst, and the molar ratio of Rac-ethyl bridged dichlorobiindan zirconium a and Rac-3-tert-butyl substituted methylene bridged dichlorobiindan zirconium B in the mixed catalyst is 1: chain shuttling polymerization with a polymerization time of 15min under the condition of 1.
The chain shuttling polymerization of this example included the following steps:
(1) weighing and preparing a chain shuttling catalyst: weighing Rac-ethyl bridged dichlorobiindane zirconium and Rac-3-tert-butyl substituted methylene bridged dichlorobiindane zirconium mixed catalyst in a molar ratio of 1:1 in a glove box by using an analytical balance, fully dissolving in toluene, and leaving behind for later use.
(2) Addition of polymerization monomers and adjustment of polymerization temperature: adding a comonomer norbornene dissolved in toluene to a polymerization reactor; introducing ethylene, wherein the ethylene pressure is 4 atm; adding toluene to flush the residual comonomer at the feeding port and leading the residual comonomer to be completely filled into the polymerization reactor; the polymerization reactor temperature was adjusted to 100 ℃.
(3) Addition of cocatalyst and chain shuttling agent: adding dry methylaluminoxane dissolved in toluene as a cocatalyst into a polymerization reactor; then adding diethyl zinc dissolved in toluene into a polymerization reactor as a chain shuttling agent, and stirring for 3-5 min; the temperature of the polymerization reactor was kept at 100 deg.C
(4) And adding a catalyst to carry out chain shuttling polymerization: keeping the temperature of the polymerization reactor at 100 ℃, quantitatively pumping the mixed catalyst prepared in the step (1) into a polymerization container by using an injector, adding toluene, flushing the residual mixed catalyst at the feeding port to ensure that the mixed catalyst is completely filled into the polymerization reactor, and carrying out polymerization reaction for 15 min. The volume ratio of the toluene to the polymerization reactor was 0.5, the molar amount of norbornene was 3mol/L relative to the volume of toluene in the polymerization reactor, and the molar ratio of cocatalyst to mixed catalyst was 2000: 1, the molar ratio of the chain shuttling agent to the mixed catalyst is 10.
(5) Termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time of 15min, opening the polymerization reactor, adding 50/1 ethanol/hydrochloric acid, and quenching the polymerization reaction;
(6) polymer solution precipitation and drying: pouring the polymer solution into a solvent, wherein the volume ratio of ethanol to hydrochloric acid is 50; 1, stirring, precipitating, filtering by a Buchner funnel, and drying for 6-8 hours in a vacuum drying oven at 60-80 ℃ to obtain the constant-weight polyolefin multi-block copolymer.
High temperature GPC analysis of the resulting polymer showed a symmetrical monomodal molecular weight distribution with a narrow variation in molecular weight distribution. DSC and related physical Properties show that chain shuttling polymerization is achieved under these conditions to give poly (ethylene-r-norbornene/ethylene) multi-block copolymers; as shown in FIG. 4 of the drawing, the melting point was 125.4 ℃ and the enthalpy was 69J/g. Nuclear magnetic analysis shows that the proportion of the catalyst, the content of soft and hard segments, the physical properties of the polymer and the like are obviously changed.
Example 6
This example shows that at a polymerization temperature of 80 ℃ and an ethylene pressure of 4atm, the molar content of diethyl zinc is 10 times that of the mixed catalyst, and the molar ratio of the mixed catalyst Rac-ethyl bridged dichlorobiindanium a to Rac-3-tert-butyl substituted methine bridged dichlorobiindanium B is 1:3, the polymerization time is 10 min.
The chain shuttling polymerization of this example included the following steps:
(1) weighing and preparing a chain shuttling catalyst: weighing Rac-ethyl bridged dichlorobiindane zirconium and Rac-3-tert-butyl substituted methylene bridged dichlorobiindane zirconium mixed catalyst in a molar ratio of 1:3 in a glove box by using an analytical balance, fully dissolving in toluene, and leaving behind for later use.
(2) Addition of polymerization monomers and adjustment of polymerization temperature: adding a comonomer norbornene dissolved in toluene to a polymerization reactor; introducing ethylene, wherein the ethylene pressure is 4 atm; adding toluene to flush the residual comonomer at the feeding port and leading the residual comonomer to be completely filled into the polymerization reactor; the polymerization reactor temperature was adjusted to 80 ℃.
(3) Addition of cocatalyst and chain shuttling agent: adding dry methylaluminoxane dissolved in toluene as a cocatalyst into a polymerization reactor; then adding diethyl zinc dissolved in toluene into a polymerization reactor as a chain shuttling agent, and stirring for 3-5 min; the temperature of the polymerization reactor is kept at 80 DEG C
(4) And adding a catalyst to carry out chain shuttling polymerization: keeping the temperature of the polymerization reactor at 80 ℃, quantitatively pumping the mixed catalyst prepared in the step (1) into a polymerization container by using an injector, adding toluene, flushing the residual mixed catalyst at a feeding port to ensure that the mixed catalyst is completely filled into the polymerization reactor, and carrying out polymerization reaction for 10 min. The volume ratio of the toluene to the polymerization reactor was 0.5, the molar amount of norbornene was 1.5mol/L relative to the volume of toluene in the polymerization reactor, and the molar ratio of cocatalyst to mixed catalyst was 2000: 1, the molar ratio of the chain shuttling agent to the mixed catalyst is 10.
(5) Termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time of 10min, opening the polymerization reactor, adding 50/1 ethanol/hydrochloric acid, and quenching the polymerization reaction;
(6) polymer solution precipitation and drying: pouring the polymer solution into a solvent, wherein the volume ratio of ethanol to hydrochloric acid is 50; 1, stirring, precipitating, filtering by a Buchner funnel, and drying for 6-8 hours in a vacuum drying oven at 60-80 ℃ to obtain the constant-weight polyolefin multi-block copolymer.
High temperature GPC analysis of the resulting polymerization showed that, as shown in FIG. 3 of the drawing, RT (min) is the time of flow-out, the left axis is dw/dlogw, the molecular weight distribution is a symmetrical monomodal distribution, the molecular weight distribution varies within a narrow range, and the DSC and related physical property studies showed that chain shuttling polymerization was achieved under these conditions to give poly (ethylene-r-norbornene/ethylene) multiblock copolymers. Nuclear magnetic analysis shows that the proportion of the catalyst, the content of soft and hard segments, the physical properties of the polymer and the like are obviously changed.
The first disclosure and disclosure of the present invention is directed to the synthesis of poly (ethylene-b-ethylene/norbornene) multi-block copolymers using chain shuttling techniques to develop high performance polyolefin block copolymer materials, and those skilled in the art can implement the methods and techniques of the present invention by referring to the contents of the disclosure, and by appropriately changing the raw materials, process conditions, and routes, etc., although the methods and techniques of the present invention have been described with reference to preferred embodiments, those skilled in the art will readily appreciate that the methods and techniques described herein can be modified or re-combined to implement the final techniques of preparation without departing from the contents, spirit and scope of the present invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. Poly (ethylene-r-norbornene/ethylene) multiblock copolymers synthesized using a chain shuttling method; the method is characterized by comprising the following steps:
(1) preparing a mixed catalyst: weighing a mixed catalyst of Rac-ethyl bridged dichlorobiindane zirconium and Rac-3-tert-butyl substituted methylene bridged dichlorobiindane zirconium, wherein the molar ratio of the mixed catalyst is 3: 1-1: 3, and dissolving the mixed catalyst in a polymerization solvent for later use;
(2) addition of polymerization monomers and adjustment of polymerization temperature: adding a comonomer norbornene dissolved in a polymerization solvent to a polymerization reactor; introducing ethylene, wherein the ethylene pressure is 1-6 atm; adjusting the temperature of a polymerization reactor to 50-100 ℃;
(3) addition of cocatalyst and chain shuttling agent: adding dry methylaluminoxane dissolved in a polymerization solvent as a cocatalyst into a polymerization reactor; then adding the diethyl zinc dissolved in the polymerization solvent into a polymerization reactor as a chain shuttling agent, and stirring for 3-5 min; keeping the temperature of the polymerization reactor at 50-100 ℃;
(4) and adding a catalyst to carry out chain shuttling polymerization: continuously keeping the temperature of the polymerization reactor at 50-100 ℃, adding the mixed catalyst solution prepared in the step (1) into a polymerization container, and polymerizing for 6-15 min;
the volume ratio of the polymerization solvent to the polymerization reactor is 1/3-2/3, the molar quantity of the norbornene is 0.2-5 mol/L relative to the volume of the polymerization solvent in the polymerization reactor, and the molar ratio of the cocatalyst to the mixed catalyst is 1000-2000: 1, the molar ratio of the chain shuttling agent to the mixed catalyst is 5-40;
(5) termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time in the step (4), opening the polymerization reactor and adding a quenching agent to quench the polymerization reaction;
(6) polymer solution precipitation and drying: and pouring the polymer solution into a precipitator, stirring, precipitating, filtering, and drying in a vacuum drying oven at 60-80 ℃ for 6-8 hours to obtain the polyolefin multi-block copolymer.
2. The multiblock copolymer according to claim 1, wherein the polymerization solvent is toluene, benzene, xylene or cyclohexane.
3. The multiblock copolymer of claim 1 wherein the polymerization solvent is toluene.
4. The multiblock copolymer according to claim 1, wherein the polymerization temperature is 50 to 70 ℃ when the ethylene pressure is 1 atm.
5. The multiblock copolymer according to claim 1, wherein the polymerization temperature is 80 to 100 ℃ when the ethylene pressure is 2 to 6 atm.
6. The multiblock copolymer according to claim 1, wherein the norbornene has a molar amount of 0.2 to 3mol/L relative to the volume of the polymerization solvent in the polymerization reactor.
7. The multiblock copolymer of claim 1, wherein the molar ratio of the cocatalyst to the hybrid catalyst is 2000: 1.
8. the multiblock copolymer according to claim 1, wherein the volume ratio of the polymerization solvent to the polymerization reactor is 1/2.
9. The multiblock copolymer according to claim 1, wherein the quenching agent and the precipitating agent are both mixed solutions of ethanol and hydrochloric acid.
10. The multiblock copolymer according to claim 9, wherein the volume ratio of the mixed solution of ethanol and hydrochloric acid is 50/1.
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