CN110655623A - Preparation of atactic polypropylene-isotactic polypropylene stereoblock polymer by chain shuttling polymerization method - Google Patents
Preparation of atactic polypropylene-isotactic polypropylene stereoblock polymer by chain shuttling polymerization method Download PDFInfo
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Abstract
The invention relates to a method for preparing atactic polypropylene-isotactic polypropylene stereoblock polymer by chain shuttling polymerization, firstly, two kinds of zirconocene metal complexes which have different stereoselectivity and similar activity to propylene under the same reaction condition are screened out, and the coordination chain transfer condition of the zirconocene metal complexes under different chain transfer agent conditions is researched. Secondly, the reversible coordination chain transfer behavior of the catalytic system was investigated. Finally, chain shuttling polymerization under the condition of a double-catalyst system/triisobutylaluminum is studied to prepare the polymer containing the atactic polypropylene-isotactic polypropylene stereoblock. The catalyst is a mixed catalyst of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride, and triisobutylaluminum is used as a chain shuttling agent to synthesize the atactic polypropylene-isotactic polypropylene stereoblock polymer.
Description
Technical Field
The invention relates to the technical field of macromolecules, and discloses a method for preparing an atactic polypropylene-isotactic polypropylene stereoblock polymer by adopting a chain shuttling polymerization method, in particular to a method for synthesizing the atactic polypropylene-isotactic polypropylene stereoblock polymer by selecting two catalysts with different stereoselectivity for propylene polymerization.
Background
Polyolefin materials are widely applied to various fields of modern life such as agricultural films, daily necessities, packaging bags, plates, pipes and the like due to the characteristics of excellent cost performance, convenient forming process, recyclability and the like, and at present, the polyolefin materials are synthetic polymer materials which are the most used and are the most widely applied. After the discovery of the ziegler-natta catalyst, various novel polyolefin catalysts, polymerization methods and polymerization processes are continuously created and applied, the molecular weight, the distribution, the stereoregularity and the like of polyolefin can be effectively regulated, in order to further expand the application range of polyolefin materials, two or more monomers are usually adopted to obtain a block copolymer by a chemical synthesis method, so as to obtain a high-performance polyolefin product, however, although a polyolefin block polymer can be obtained by utilizing the traditional active coordination polymerization, the sequence and the number of the block length can be effectively regulated, but one active catalyst can only generate one polyolefin molecular chain, and the use efficiency of the catalyst is low; the structure of the block copolymer can only be controlled by different feeding sequences, and the commercial value is low, thereby limiting the application of the method.
At present, most of polyolefin industrial products in China are common general materials, and high-end polyolefin products almost completely depend on import. Therefore, a new polymerization process needs to be explored urgently, so that the performance of the polyolefin is continuously improved, and a new high-performance polyolefin product with independent intellectual property rights in China is developed. Chain shuttling polymerization is a novel coordination polymerization method developed in the last decade, can efficiently prepare polyolefin block copolymers, can effectively control the molecular weight and the distribution of the polymers, obtains multi-block copolymer materials with more excellent comprehensive properties, and develops novel polyolefin materials. A series of multi-block polyolefin products obtained by the dow chemical company using this technology occupy monopoly of the international market.
Chain shuttling copolymerization is a coordination polymerization method developed on the basis of reversible coordination chain transfer polymerization, which is widely concerned by high-molecular chemists due to high efficiency and reversibility and is reversible
The coordination chain transfer can not only effectively control the molecular weight and the molecular weight distribution of the polymer, but also be used for preparing the block olefin copolymer and the end group functionalized polyolefin material. However, simple reversible coordination chain transfer polymerization is difficult to use for the synthesis of multi-block olefin copolymers and cannot be used for the industrial production of new polyolefin materials. The mechanism of chain shuttling polymerization is that during the polymerization process, active chains alternately grow among catalyst active centers with obvious differences through a chain shuttling agent, and then a multi-block copolymer is generated.
The concept of chain shuttling was first proposed by the developer of Dow Chemical in 2006. The required catalyst and chain transfer agent are screened out by adopting a high-throughput method, the bisphenol oxygen amine zirconium with weaker copolymerization capability and the pyridine imine hafnium with stronger copolymerization capability are finally determined to be used as a double-catalytic polymerization system after primary and secondary screening, the diethyl zinc is used as a chain transfer agent, a continuous processing technology is adopted to prepare the multi-block copolymer with a high-density polyethylene chain segment (hard segment) and an amorphous ethylene/octene random copolymerization chain segment alternating (soft segment), the function relation between the melting point and the density is established by gel permeation chromatography, the performances of the ethylene-octene random copolymer and the multi-block copolymer prepared by experiments are compared in detail, and the obtained multi-block copolymer has good transparency, narrow molecular weight distribution and excellent elastic property, can be used at high temperature, and further widens the application range of the polyolefin material.
In 2007, Busico in Italy and Dow company work together, and isotactic polypropylene and syndiotactic polypropylene chains are synthesized by using two chiral enantiomers of a hafnium pyridine imine catalyst and trimethylaluminum to form a catalyst systemSegmented block copolymers. Same year, Antti[9]The inventors prepared novel polypropylene by using diphenylmethyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride and dimethylsilylbis (4-tert-butyl-2-methylcyclopentadienyl) zirconium dichloride as catalysts and trimethylaluminum as a chain shuttling agent, and studied the catalytic activity, molecular weight, distribution and thermodynamic properties of the dual catalyst system respectively to obtain strong evidence of shuttling by repeated extraction of the polymer and analysis of the tacticity of the polymer.
The novel linear-hyperbranched polyethylene multi-block copolymer is synthesized by chain walking and chain shuttling polymerization by using ethylene as a monomer, organic nickel and organic zirconium as catalysts, methylaluminoxane as a cocatalyst and diethyl zinc as a chain transfer agent through Wang Li professor of Zhejiang university, and the obtained polymer has narrow molecular weight distribution, high melting point and comprehensive excellent properties of linear and branched polyethylene, so that the efficient and economic preparation of the polyolefin material by using one monomer becomes possible. Pan et al complete the synthesis of a multi-block copolymer of polystyrene segments and poly-conjugated diene segments by using different scandium metal catalysts (scandium 1, scandium 2, scandium 3) with triisobutylaluminum as chain shuttling agent. Synthesizing syndiotactic polystyrene-cis-1, 4-polyisoprene under the action of scandium 1/scandium 2/triisobutyl aluminum; the syndiotactic polystyrene-3, 4-polyisoprene is synthesized under the action of scandium 1/scandium 3/triisobutyl aluminum, and the chain shuttling polymerization reaction of the conjugated diene catalyzed by the rare earth catalyst is realized for the first time.
A French scientist Zinck synthesizes a novel thermoplastic elastomer polystyrene-trans-1, 4-polyisoprene multi-block copolymer by adopting a half-sandwich lanthanum complex for catalyzing isoprene polymerization with high activity and a ansa-type sandwich neodymium complex for catalyzing styrene polymerization with high activity as catalysts and taking alkyl magnesium as a chain transfer agent. The Chimonanthus praecox task group firstly obtains a conclusion that the chain transfer efficiency is determined by the matching degree of metal active centers and the metal carbon bond strength of a chain transfer agent through researching the chain transfer polymerization process of isoprene under the action of a lanthanide metal catalyst, a cocatalyst borate and a chain transfer agent triisobutyl aluminum. Meanwhile, the transfer efficiency of catalyzing 1,4 polymerization is the highest when the triisobutyl aluminum and scandium are mixed in a ratio of 10:1, and the transfer efficiency of catalyzing 3,4 polymerization is very high when the triisobutyl aluminum and lutetium are in a wide ratio range. The catalytic polymerization reaction kinetics of scandium and lutetium are analyzed in detail by using Chimonanthus praecox and the like, and chain transfer constants of the two reactions are similar and the two reactions can be used as two catalysts for chain shuttling polymerization reaction. And finally, under copolymerization conditions, selecting scandium and lutetium metal catalysts with the same ligand, a cocatalyst borate and a chain transfer agent triisobutyl aluminum, and taking isoprene as a monomer to prepare the novel polyolefin material with different distributions of 1, 4-polyisoprene and 3, 4-polyisoprene. Unlike the previously published papers using two or more monomers, the Chimonanthus praecox group uses only one conjugated diene to synthesize a multi-block copolymer, which provides a new research direction.
Chain shuttling polymerization has been widely paid attention by polymer scientists because it has incomparable advantages in polymer topology design, molecular weight control, catalyst utilization rate and other aspects. The chain shuttling polymerization method is beneficial to the industrialized production of novel polyolefin materials, obtains multi-block copolymers with more excellent comprehensive performance, greatly widens the application field of the polyolefin materials, and can really realize chain shuttling polymerization and obtain the research yield index of the multi-block copolymers, namely ethylene and alpha-olefin multi-block copolymers with different brands reported by the Dow chemical company and polystyrene-trans-1, 4-polyisoprene multi-block copolymers reported by Zinck.
Disclosure of Invention
The technical problem to be solved by the invention is to solve the state of the prior art; firstly, two kinds of zirconocene metal complexes with different stereoselectivity and similar activity to propylene under the same reaction condition are screened out, and the coordination chain transfer condition of the zirconocene metal complexes under different chain transfer agent conditions is researched. Secondly, the reversible coordination chain transfer behavior of the catalytic system was investigated. Finally, chain shuttling polymerization under the condition of a double-catalyst system/triisobutylaluminum is studied to prepare the polymer containing the atactic polypropylene-isotactic polypropylene stereoblock.
The technical scheme of the invention is as follows:
synthesizing stereoblock polypropylene by using a chain shuttling method; the method is characterized by comprising the following steps:
(1) preparing a mixed catalyst: a mixed catalyst of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (commercial) and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride was weighed out in a molar ratio of 1:1, dissolving the mixture by using a polymerization solvent to prepare a catalyst solution;
(2) preparing a cocatalyst: weighing dry methylaluminoxane, dissolving by using a polymerization solvent, and preparing a cocatalyst solution;
(3) adjusting polymerization temperature and propylene pressure: introducing propylene into a polymerization reactor, wherein the propylene pressure is 1-6 atm, and the temperature of the polymerization reactor is kept at 70-90 ℃;
(4) addition of cocatalyst and chain shuttling agent: adding the cocatalyst prepared in the step (2) into a polymerization reaction container; adding triisobutyl aluminum serving as a chain shuttling agent into a polymerization reaction container, and stirring for 3-5 min; keeping the polymerization reaction temperature at 70-90 ℃;
(5) and adding a catalyst to carry out chain shuttling polymerization: continuously keeping the temperature of the polymerization reactor at 70-90 ℃, adding the mixed catalyst solution prepared in the step (1) into a polymerization reaction container, and polymerizing for 10-60 min;
(6) and terminating the polymerization reaction: opening a polymerization reaction container, adding an ethanol/hydrochloric acid solution, and quenching the polymerization reaction;
(7) polymer solution precipitation and drying: and pouring the polymer solution into a mixed solution of ethanol and hydrochloric acid, stirring, precipitating, filtering by using a Bush funnel, and drying for 6-8 hours at the temperature of 60-80 ℃ in a vacuum drying oven to obtain the polymer.
The volume ratio of the total solvent of the polymerization system to the polymerization reactor in all the steps is 1/3-2/3.
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 100-250: 1.
the steps (1) and (2) are the same polymerization solvent, and the polymerization solvent is toluene, benzene, xylene or cyclohexane; the preferred polymerization solvent is toluene.
Preferably, the molar ratio of the cocatalyst to the catalyst is 1500: 1;
preferably, the total polymerization solvent is 1/2 which is the volume ratio of the polymerization reactor;
the advantages and effects of the invention are illustrated as follows:
(1) the invention screens out two catalysts with similar structures and different stereoselectivities by reading literatures and experiments, namely diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (commercialized) and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride (synthesized according to the literatures);
(2) by selecting triisobutylaluminum as a chain shuttling agent and utilizing a chain shuttling method proposed by Dow Chemical company, an atactic polypropylene-isotactic polypropylene stereoblock polymer is synthesized for the first time by using a diphenyl methylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride synthesized amorphous polypropylene chain segment as a soft segment and a dimethyl silicon-based bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride synthesized isotactic polypropylene chain segment as a hard segment.
(3) The polymer obtained by polymerization is confirmed to contain amorphous polypropylene-isotactic polypropylene stereoblock polymer 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 distribution thereof by high temperature GPC, DSC, and the like. We find that the polymer has two melting points, the melting point range is 100-110 ℃, 140-150 ℃, and the polymer has higher elongation at break.
The invention adopts two kinds of metallocene catalysts with different stereoselectivity for propylene polymerization, optimizes polymerization conditions, screens out chain transfer agent matched with the system, and obtains polymer with unimodal distribution by chain shuttling polymerization technology. 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 4 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 atactic polypropylene-isotactic polypropylene stereoblock polymers, all moisture and oxygen sensitive operations are performed by those skilled in the art under nitrogen protection in MBraun glove box or 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 (Q2000DSC) at a ramp-up/ramp-down rate of 20 deg.C/min in a nitrogen atmosphere. GelThe chromatography was carried out by means of a gel permeation chromatograph model PL GPC-220. The tester is RI-Laser, the packed column is Plgel 10 μm MIXED-BLS, 1,2, 4-Trichlorobenzene (TCB) is used as solvent (0.05 wt% of 2, 6-di-tert-butyl-4-methylphenol is added as antioxidant), the testing temperature is 150 ℃, the flow rate is 1.0mL/min, and PL EasiCal PS-1 is used as a standard sample.
Two catalysts selected in the present invention, diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, purchased from inokay, and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride, were synthesized according to the related literature (Organometallics 2000,19(4),420 american chemical society ACS database).
Synthesis route of dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopentyl [2,3-b ] thiophen-6-yl) zirconium dichloride
3-bromo-2-methylthiophene (1) to a 500mL vial was added 25g (153mmol) of 3-bromothiophene, degassed by freezing at-78 deg.C, followed by addition of 60mL of tetrahydrofuran, 76.5mL (2M,153mmol) of lithium diisopropylamide was slowly added dropwise after dissolution, and the solution was brought to 0 deg.C (ice bath) and stirred for 30 minutes. Immediately thereafter, the reaction temperature was lowered to-78 deg.C, 10mL (161mmol) of methyl iodide was added, and stirring was carried out at-78 deg.C for 30 minutes, followed by warming to room temperature and stirring for 1 hour. The organic layer was dried over anhydrous magnesium sulfate for 20 minutes, filtered, and the solvent was evaporated with a rotary evaporator. The yield was 90%.1H NMR(CDCl3):δ7.1(d,1H),6.9(d,1H),2.4(s,3H).
2-methyl-3- (2-methylphenyl) thiophene (2) to a mixture containing 27g (153mmol) of (1) and 0.3g of [ bis (diphenylphosphino) propane ]]7.6mL of o-tolyl magnesium bromide (2M,153mmol) was added dropwise to the solution of nickel dichloride in tetrahydrofuran. After the addition was complete, the reaction flask was stirred at 0 ℃ for 1 hour, then warmed to room temperature, and the mixture was stirred overnight before quenching with water. The organic portion was extracted with dichloromethane, dried over magnesium sulfate and chromatographed using petroleum ether developing solvent. Yield ofThe content was 90%.1H NMR(CDCl3):δ7.2-7.4(m,4H),7.18(t,1H),6.98(t,1H),2.35(d,3H),2.27(d,3H).
2, 5-dimethyl-3- (2-methylphenyl) -5, 6-dihydrocyclopenta [1,2-b]Thiophene-4-one (3) A solution of 15g (2) (80mmol), 8g (92mmol) of methacrylic acid and 20mL of dichloromethane was slowly added to 200g of polyphosphoric acid at 80 ℃ and after stirring for 5 hours the reaction mixture was quenched by pouring into ice water. The organic layer was collected with dichloromethane and washed with saturated sodium bicarbonate solution. The organic layer was dried over magnesium sulfate and filtered, and finally the solvent was dried in vacuo to give a reddish brown oil. The product can be directly used for the next reaction without purification.1H NMR(CDCl3):δ7.1-7.3(m,3H),7.0(d,1H),2.7-3.0(m,2H),2.25(s,3H)，2.18(m,1H),2.05(s,3H),1.2(d,3H).
2, 5-dimethyl-3- (2-methylphenyl) -6-hydrocyclopenta [1,2-b ]]Thiophene (4) 9.8g (38.5mmol) of (4) were first dissolved in 40mL of tetrahydrofuran solution, and then 7.8mL (2.5M) of lithium aluminum hydride was slowly added dropwise to (4) at 0 ℃ and stirred at room temperature for 3 hours, then the reaction was quenched with ice water, filtered, then extracted with dichloromethane, dried over magnesium sulfate, filtered and the solvent was evaporated. The crude product was dissolved in 40mL of toluene, and 0.3g of p-toluenesulfonic acid was added and stirred at 70 ℃ for 1.5 hours. The reaction was quenched with sodium bicarbonate solution (50mL), extracted with petroleum ether, and chromatographed using petroleum ether developing solvent. The yield was 68%.1HNMR(CDCl3):δ7.1-7.3(m,4H),6.7(m,1H),6.4(m,1H),3.6(s,2H),3.2(ss,2H),2.6(s,3H),2.55(s,3H),2.47(s,3H),2.46(s,3H),2.42(s,3H),2.40(s,3H).
Bis (2, 5-dimethyl-3- (2-methylphenyl) -6-hydrocyclopenta [2,3-b ] thiophen-6-yl) dimethylsilane (5) (4) (6.7g, 28mmol) was dissolved in 40mL of tetrahydrofuran at-78 ℃, n-butyllithium (12mL,2.4M) was slowly added dropwise, the temperature was slowly raised to room temperature, and after stirring at room temperature for 16 hours, dichlorodimethylsilane (1.4mL, 14.7mmol) was added dropwise to the solution with stirring at-78 ℃. The reaction mixture was slowly warmed to room temperature and stirred for 2 days. Extraction with dichloromethane, drying over magnesium sulfate, filtration, evaporation of the solvent, separation with petroleum ether: ethyl acetate (20:1) developing agent column chromatography, the yield is 30%.
Preparation of Complex (6) into a 100mL mouth-branched bottle were added (5) (2.16g,4mmol) and 50mL of anhydrous ether, n-butyllithium (5mL,1.6M) was added at-78 ℃, slowly warmed to room temperature, reacted at room temperature for 2 hours, then the solvent was drained, 30mL of n-hexane was added, zirconium tetrachloride (0.9g,4mmol) was poured into the reaction system through a tee, slowly warmed to room temperature, reacted for 16 hours, the solvent was drained, dissolved in dichloromethane, filtered, the dichloromethane was drained, repeatedly washed with n-hexane, and the n-hexane was drained. The yield is 60%.1H NMR(CD2Cl2):δ7.65(m,2H,meso),7.60(m,2H,rac),7.27(m,6H,meso),7.26(m,6H,rac),6.33(s,2H,rac),6.18(s,2H,meso),2.34(s,6H,rac),2.32(s,6H,meso),2.30(s,6H,rac),2.25(s,6H,meso),2.09(s,6H,rac),2.03(s,6H,meso),1.17(s,3H,meso),1.13(s,3H,meso),1.08(s,6H,rac).
Example 1
This example shows that at a polymerization temperature of 70 ℃ and a propylene pressure of 1atm, the molar content of triisobutylaluminum is 100 times that of the mixed catalyst, and the molar ratio of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride is 1:1 for 30min, using a polymerization reactor volume of 100mL and a total toluene volume of 1/3 parts of the polymerization reactor volume.
The chain shuttling polymerization of this example included the following steps:
(1) weighing and preparing a chain shuttling catalyst: diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride 2.5 mu mol and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride 2.5 mu mol are weighed in a glove box by an analytical balance, the molar ratio is 1:1, and the solution is dissolved by 10mL of toluene to prepare a catalyst solution.
(2) Preparing a cocatalyst: weighing 7500 mu mol of dry methylaluminoxane, dissolving with 10mL of toluene, and preparing into a cocatalyst solution;
(3) adjusting polymerization temperature and propylene pressure: introducing propylene into a polymerization reactor, wherein the pressure of the propylene is 1atm, and the temperature of the polymerization reactor is kept at 70 ℃;
(4) addition of cocatalyst and chain shuttling agent: adding all the prepared cocatalyst in the step (2) into a polymerization reactor; subsequently, 500 mu mol of chain shuttling agent triisobutyl aluminum is added into the polymerization reaction vessel and stirred for 5 min; maintaining the polymerization reactor temperature at 70 ℃;
(5) and adding a catalyst to carry out chain shuttling polymerization: keeping the temperature of the polymerization reactor at 70 ℃, quantitatively extracting 10mL of the mixed catalyst prepared in the step (1) by using an injector, adding the mixed catalyst into the polymerization reactor, adding 13mL of toluene, flushing the residual mixed catalyst at the feeding port to ensure that the mixed catalyst is completely added into the polymerization reactor, and carrying out polymerization reaction for 30 min;
(6) termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time of 30min, opening the polymerization reactor, adding an ethanol/hydrochloric acid solution with the volume ratio of 50/1, and quenching the polymerization reaction;
(7) polymer solution precipitation and drying: all polymer solutions were poured into the prepared ethanol/hydrochloric acid 50: 1, the solution was stirred to precipitate, filtered through a buchner funnel, and dried in a vacuum oven at 80 ℃ for 8 hours to obtain a constant weight polymer.
High temperature GPC analysis of the resulting polymerization showed logM on the abscissa as shown in FIG. 1 of the figure descriptionwAnd the left coordinate axis is dw/dlogw, the molecular weight distribution is symmetrical unimodal distribution, and the molecular weight distribution is changed in a narrow range, so that the amorphous polypropylene-isotactic polypropylene stereoblock copolymer is obtained.
Example 2
In this example, the polymerization temperature was 70 ℃, the propylene pressure was 1atm, the molar content of triisobutylaluminum was 250 times that of the mixed catalyst, and the molar ratio of the mixed catalyst 1 to the catalyst 2 was 1:1 for 30min, 100mL polymerization flask reactor was used, and the total volume of benzene was 1/2 times the volume of the polymerization reactor.
The chain shuttling polymerization of this example included the following steps:
(1) weighing and preparing a chain shuttling catalyst: weighing 2.5 mu mol of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride and 2.5 mu mol of a dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride mixed catalyst in a molar ratio of 1:1 by using an analytical balance in a glove box, and fully dissolving the mixture by using 10mL of benzene to prepare a catalyst solution;
(2) preparing a cocatalyst: weighing 7500 mu mol of dry methylaluminoxane, dissolving with 10mL of benzene, and preparing into a cocatalyst solution;
(3) adjusting polymerization temperature and propylene pressure: introducing propylene into a polymerization reactor, wherein the propylene pressure is 1atm, and the temperature of the polymerization reactor is adjusted to 70 ℃;
(4) addition of cocatalyst and chain shuttling agent: adding all the prepared cocatalyst in the step (2) into a polymerization reactor; 1250 mu mol of chain shuttling agent triisobutyl aluminum is added into a polymerization reactor and stirred for 3 min; maintaining the polymerization reactor temperature at 70 ℃;
(5) and adding a catalyst to carry out chain shuttling polymerization: keeping the temperature of the polymerization reactor at 70 ℃, quantitatively extracting 10mL of the mixed catalyst prepared in the step (1) by using an injector, adding the mixed catalyst into the polymerization reactor, adding 30mL of benzene, and flushing the residual mixed catalyst at the feeding port to ensure that the mixed catalyst is completely added into the polymerization reactor, wherein the polymerization reaction time is 30 min;
(6) termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time of 30min, opening the polymerization reactor, adding an ethanol/hydrochloric acid solution with the volume ratio of 50/1, and quenching the polymerization reaction;
(7) polymer solution precipitation and drying: all polymer solutions were poured into the prepared ethanol/hydrochloric acid solution of 50/1, stirred to precipitate out, filtered through a buchner funnel, and dried in a vacuum oven at 60 ℃ for 6 hours to constant weight polymer.
High temperature GPC analysis of the resulting polymerization showed that the abscissa of the graph is logM, as shown in FIG. 2wAnd the left coordinate axis is dw/dlogw, the molecular weight distribution is symmetrical monomodal distribution, and the molecular weight distribution changes in a narrow range, which indicates that chain shuttling polymerization is realized under the condition to obtain the amorphous polypropylene-isotactic polypropylene stereoblock polymer.
Example 3
In this example, diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride mixed catalysts were weighed at a polymerization temperature of 90 ℃ and a propylene pressure of 1atm, with a molar content of triisobutylaluminum being 150 times that of the mixed catalysts, and a chain shuttle polymerization having a molar ratio of 1:1 and a polymerization time of 60min was carried out, and the volume of the polymerization reactor used was 100mL, and the total volume of xylene was 1/2 of the volume of the polymerization reactor.
The chain shuttling polymerization of this example included the following steps:
(1) weighing and preparing a chain shuttling catalyst: weighing 2.5 mu mol of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride and 2.5 mu mol of a dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride mixed catalyst in a molar ratio of 1:1 in an analytical balance in a glove box, and fully dissolving the mixture in 10mL of dimethylbenzene to prepare a catalyst solution;
(2) preparing a cocatalyst: weighing 5000 mu mol of dry methylaluminoxane, dissolving with 10mL of dimethylbenzene, and preparing a cocatalyst solution;
(3) adjusting polymerization temperature and propylene pressure: introducing propylene into a polymerization reactor, wherein the propylene pressure is 1atm, and the temperature of the polymerization reactor is adjusted to 90 ℃;
(4) addition of cocatalyst and chain shuttling agent: adding all the prepared cocatalyst in the step (2) into a polymerization reactor; adding 750 mu mol of chain shuttling agent triisobutyl aluminum into a polymerization reactor, and stirring for 5 min; maintaining the polymerization reactor temperature at 90 ℃;
(5) and adding a catalyst to carry out chain shuttling polymerization: keeping the temperature of the polymerization reactor at 90 ℃, quantitatively extracting 10mL of the mixed catalyst prepared in the step (1) by using a syringe, adding the mixed catalyst into the polymerization reactor, adding 30mL of dimethylbenzene, and flushing the residual mixed catalyst at the feeding port to ensure that the mixed catalyst is completely added into the polymerization reactor, wherein the polymerization reaction time is 60 min.
(6) Termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time of 60min, opening the polymerization reactor, adding an ethanol/hydrochloric acid solution with the volume ratio of 50/1, and quenching the polymerization reaction;
(7) polymer solution precipitation and drying: all polymer solutions were poured into a prepared ethanol/hydrochloric acid solution at a volume ratio of 50/1, the solution was stirred to precipitate out, filtered through a buchner funnel, dried at 70 ℃ in a vacuum oven for 7 hours to constant weight polymer.
High temperature GPC analysis of the obtained polymer shows that the molecular weight distribution is symmetrical monomodal distribution, the molecular weight distribution varies in a narrow range, and DSC study shows that chain shuttling polymerization is realized under the conditions to obtain the atactic polypropylene-isotactic polypropylene stereoblock polymer.
Example 4
This example is a mixed catalyst of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride in a molar ratio of 1:1 for 30min, a 200mL polymerization reactor volume and a total cyclohexane volume of 1/2 parts of the polymerization reactor volume.
The chain shuttling polymerization of this example included the following steps:
(1) weighing and preparing a chain shuttling catalyst: diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride 2.5 mu mol and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride mixed catalyst 2.5 mu mol are weighed in a glove box by an analytical balance, the molar ratio is 1:1, and the mixed catalyst is dissolved in 10mL of cyclohexane to prepare catalyst solution.
(2) Preparing a cocatalyst: weighing 1500 mu mol of dry methylaluminoxane, dissolving with 10mL of cyclohexane, and preparing into a cocatalyst solution;
(3) adjusting polymerization temperature and propylene pressure: introducing propylene into a polymerization reactor, wherein the propylene pressure is 6atm, and the temperature of the polymerization reactor is adjusted to 70 ℃;
(4) addition of cocatalyst and chain shuttling agent: adding all the prepared cocatalyst in the step (2) into a polymerization reactor; adding 100 mu mol of chain shuttling agent triisobutyl aluminum into a polymerization reactor, and stirring for 4 min; maintaining the polymerization reactor temperature at 70 ℃;
(5) and adding a catalyst to carry out chain shuttling polymerization: keeping the temperature of the polymerization reactor at 70 ℃, quantitatively extracting 2mL of the mixed catalyst prepared in the step (1) by using a syringe, adding the mixed catalyst into the reaction kettle, adding 88mL of cyclohexane, flushing the residual mixed catalyst at the feeding port, and enabling the mixed catalyst to be completely filled into the polymerization reactor, wherein the polymerization reaction time is 30 min.
(6) Termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time of 30min, opening the polymerization reactor, adding an ethanol/hydrochloric acid solution with the volume ratio of 50/1, and quenching the polymerization reaction;
(7) polymer solution precipitation and drying: all polymer solutions were poured into the prepared solution with a volume ratio of ethanol/hydrochloric acid of 50/1, precipitated by stirring, filtered through a Buchner funnel, dried in a vacuum oven at 80 ℃ for 8 hours to constant weight polymer.
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 property studies show that chain shuttling polymerization is realized under the conditions to obtain amorphous polypropylene-isotactic polypropylene block copolymer; as shown in figure 4 of the drawing, there are two melting points of 110 deg.C and 159 deg.C, respectively, corresponding to enthalpy changes of 13.2 and 26.1J/g.
Example 5
This example shows that at a polymerization temperature of 70 ℃ and a propylene pressure of 6atm, the molar content of triisobutylaluminum is 100 times that of the mixed catalyst, diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride in a molar ratio of 1:1 for 45min, 200mL of polymerization reactor and 1/2 for the total volume of toluene.
The chain shuttling polymerization of this example included the following steps:
(1) weighing and preparing a chain shuttling catalyst: diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride 2.5. mu. mol and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride 2.5. mu. mol were weighed in a glove box using an analytical balance, the molar ratio was 1:1, and the catalyst solution was prepared by dissolving with 10mL of toluene sufficiently.
(2) Preparing a cocatalyst: weighing 1500 mu mol of dry methylaluminoxane, dissolving with 10mL of toluene, and preparing a cocatalyst solution;
(3) adjusting polymerization temperature and propylene pressure: introducing propylene into a polymerization reactor, wherein the propylene pressure is 6atm, and the temperature of the polymerization reactor is adjusted to 70 ℃;
(4) addition of cocatalyst and chain shuttling agent: adding all the prepared cocatalyst in the step (2) into a polymerization reactor; adding 100 mu mol of chain shuttling agent triisobutyl aluminum into a polymerization reactor, and stirring for 3 min; maintaining the polymerization reactor temperature at 70 ℃;
(5) and adding a catalyst to carry out chain shuttling polymerization: keeping the temperature of the polymerization reactor at 70 ℃, quantitatively extracting 2mL of the mixed catalyst prepared in the step (1) by using a syringe, adding the mixed catalyst into the polymerization reactor, adding 88mL of toluene, flushing the residual mixed catalyst at the feeding port to ensure that the mixed catalyst is completely added into the polymerization reactor, and carrying out polymerization reaction for 45 min.
(6) Termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time of 45min, opening the polymerization reactor, adding an ethanol/hydrochloric acid solution with the volume ratio of 50/1, and quenching the polymerization reaction;
(7) polymer solution precipitation and drying: all the polymer solution was poured into the prepared solution with a volume ratio of ethanol/hydrochloric acid solution of 50/1, stirred to precipitate out, filtered through a Buchner funnel, and dried in a vacuum oven at 80 ℃ for 8 hours to obtain a constant weight polymer.
High temperature GPC analysis of the resulting polymerization showed logM on the abscissa as shown in FIG. 3 of the drawingwThe left coordinate axis is dw/dlogw, the molecular weight distribution is in pairsThe research on the distribution of the molecular weight, namely the unimodal distribution, changes in a narrow range, DSC and related physical properties shows that chain shuttling polymerization is realized under the condition to obtain the amorphous polypropylene-isotactic polypropylene stereoblock copolymer, and nuclear magnetic analysis shows that the content of the block is obviously changed by changing the polymerization time.
Example 6
This example shows that at a polymerization temperature of 80 ℃ and a propylene pressure of 4atm, the molar content of triisobutylaluminum is 100 times that of the mixed catalyst, diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride in a molar ratio of 1:1 for 10min, a 200mL polymerization reactor volume and a total toluene volume of 2/3 parts of the polymerization reactor volume.
The chain shuttling polymerization of this example included the following steps:
(1) weighing and preparing a chain shuttling catalyst: diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride 2.5 mu mol and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride mixed catalyst 2.5 mu mol are weighed in a glove box by an analytical balance, the molar ratio is 1:1, and 10mL of toluene is fully dissolved to prepare catalyst solution.
(2) Preparing a cocatalyst: weighing 2000 mu mol of dry methylaluminoxane, dissolving the methylaluminoxane by using 10mL of toluene, and preparing a cocatalyst solution;
(3) adjusting the polymerization temperature and the polymerization pressure: feeding propylene into the polymerization reactor, wherein the pressure of the propylene is 4 atm; the polymerization reactor temperature was adjusted to 80 ℃.
(4) Addition of cocatalyst and chain shuttling agent: adding all the prepared cocatalyst in the step (2) into a polymerization reactor; adding 100 mu mol of chain shuttling agent triisobutyl aluminum into a polymerization reactor, and stirring for 3 min; maintaining the polymerization reactor temperature at 80 ℃;
(5) and adding a catalyst to carry out chain shuttling polymerization: keeping the temperature of the polymerization reactor at 80 ℃, quantitatively extracting 2mL of the mixed catalyst prepared in the step (1) by using a syringe, adding the mixed catalyst into the polymerization reactor, adding 121mL of toluene, flushing the residual mixed catalyst at the feeding port to ensure that the mixed catalyst is completely added into the polymerization reactor, and carrying out polymerization reaction for 10 min.
(6) Termination of the polymerization reaction: after the polymerization reaction reaches the polymerization time of 10min, opening the polymerization reactor, adding an ethanol/hydrochloric acid solution with the volume of 50/1, and quenching the polymerization reaction;
(7) polymer solution precipitation and drying: all polymer solutions were poured into the prepared solution with a volume ratio of ethanol/hydrochloric acid of 50/1, stirred to precipitate out, filtered through a Buchner funnel, dried in a vacuum oven at 80 ℃ for 8 hours to constant weight polymer.
High temperature GPC analysis of the obtained polymerization shows that the molecular weight distribution is symmetrical monomodal distribution, the molecular weight distribution varies in a narrow range, and DSC study shows that chain shuttling polymerization is realized under the conditions to obtain the atactic polypropylene-isotactic polypropylene stereoblock copolymer.
The synthesis of atactic polypropylene-isotactic polypropylene stereoblock polymers using chain shuttling techniques to develop high performance polyolefin block copolymer materials as disclosed and claimed herein can be accomplished by those skilled in the art by appropriate modification of the starting materials, process conditions, routes, etc. in view of the present disclosure. 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 (6)
1. Synthesizing an atactic polypropylene-isotactic polypropylene stereoblock polymer by using a chain shuttling method; the method is characterized by comprising the following steps:
(1) weighing a mixed catalyst of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride and dimethylsilyl bridged bis (2, 5-dimethyl-3- (2-methylbenzene) -cyclopenta [2,3-b ] thiophen-6-yl) zirconium dichloride, wherein the molar ratio of the mixed catalyst is 1:1, dissolving the mixture by using a polymerization solvent to prepare a catalyst solution;
(2) weighing dry methylaluminoxane, dissolving by using a polymerization solvent, and preparing a cocatalyst solution;
(3) introducing propylene into a polymerization reactor, wherein the propylene pressure is 1-6 atm, and the temperature of the polymerization reactor is kept at 70-90 ℃;
(4) adding the cocatalyst prepared in the step (2) into a polymerization reaction container; adding triisobutyl aluminum serving as a chain shuttling agent into a polymerization reaction container, and stirring for 3-5 min; keeping the polymerization reaction temperature at 70-90 ℃;
(5) continuously keeping the temperature of the polymerization reactor at 70-90 ℃, adding the mixed catalyst solution prepared in the step (1) into a polymerization reaction container, and polymerizing for 10-60 min;
(6) opening a polymerization reaction container, adding a mixed solution of ethanol and hydrochloric acid, and quenching the polymerization reaction;
(7) and pouring the polymer solution into a container containing a mixed solution of ethanol and hydrochloric acid, stirring, precipitating, filtering, and drying in a vacuum drying oven at 60-80 ℃ for 6-8 hours to obtain the polymer.
2. The method of claim 1, wherein the molar ratio of the cocatalyst to the mixed catalyst is 1000 to 2000: 1.
3. the method of claim 1, wherein the molar ratio of chain shuttling agent to mixed catalyst is 100 to 250: 1.
4. the process according to claim 1, wherein the polymerization solvent used in steps (1) and (2) is toluene, benzene, xylene or cyclohexane.
5. The method as set forth in claim 1, wherein the mixing ratio of the ethanol and hydrochloric acid is 50/1.
6. The method according to claim 1, wherein the volume ratio of the total solvent in the polymerization system to the polymerization reactor is from 1/3 to 2/3.
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