CN106008766A - Composite metallocene catalyst for norbornene polymerization and preparation method thereof - Google Patents
Composite metallocene catalyst for norbornene polymerization and preparation method thereof Download PDFInfo
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- 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
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
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- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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Abstract
The invention relates to a composite metallocene catalyst for norbornene polymerization and a preparation method thereof, belonging to the technical field of polymeric material preparation. By using a metallocene compound as a core component, the metallocene compound and lithium chloride are compounded according to the mole ratio of (1-2):(2-1). The synthetic process of the composite metallocene catalyst is simple; the synthesized product can be easily extracted; and the catalyst has high purification rate, and can be recycled by recrystallization. Meanwhile, the catalyst has excellent catalytic activity in norbornene polymerization; and the obtained polymer has the advantages of narrow molecular weight distribution and excellent properties, and has higher actual application prospects.
Description
Technical field
The present invention relates to a kind of composite metallocene catalyst for norbornene polymerization and preparation method thereof, belong to
In polymeric material preparing technical field.
Background technology
Metallocene catalyst is with the difference of traditional catalyst maximum: metallocene catalyst only one of which activity
Center, its metallic atom typically all in the environment of restricted, only allows a polymer monomer to enter catalysis
On agent active site.Relative molar mass, relative molar mass distribution, comonomer is controlled therefore, it is possible to accurate
Content and the distribution on main chain and clean structure etc..Its polymer is the polymerization of a kind of high stereoregularity
Thing, molecular weight distribution is the narrowest.
The feature of metallocene catalyst single active center, can make any polymerizing olefin monomers, it is possible to achieve the past is solid
The polymerization of body catalyst can not be polymerized or catalytic efficiency is extremely low cycloolefin, conjugated diene and polar monomer or
Copolyreaction, thus more high performance synthetic material can be developed.Another feature of metallocene catalyst, is can
Accurately control polymerization process so that it is structure and the uniform polymer of performance can be produced continuously, can set by user's requirement
Meter properties of product.
Norbornene polymer is the polymer of a kind of excellent performance, is widely used in multiple fields, in the modern times
Industry especially has in terms of coating material, protection and film forming thereof bigger application.In recent years, China
Start norbornene polymerization is studied, the most flourish in the whole nation, except norborene, one
The polymerization of a little norbornene derivatives is also in fast development, to meet the industrial demand to this type of material.
But, along with the industrial requirement to norbornene polymer performance is more and more higher, different metallocenes obtains
Polymerization product have a biggest performance difference, major part performance is difficult to meet the demand of people, therefore, just
Need to develop the product that performance is more excellent.
Summary of the invention
It is an object of the invention to overcome above-mentioned weak point, it is provided that a kind of being combined for norbornene polymerization
Metallocene catalyst and preparation method thereof.
The technical scheme provided according to the present invention, a kind of composite metallocene catalyst for norbornene polymerization,
It is with metallocene compound as nucleus, by metallocene compound and lithium chloride according to the mol ratio of 1-2:2-1
Compounding.
The concrete structure of described wherein metallocene compound is as follows:
Wherein R=Me, Et or Cl.
The preparation method of the described composite metallocene catalyst for norbornene polymerization, enters as follows
OK:
(1) reaction: take (indenyl) TiI3It is dissolved in the THF solution of excess, protects at-35 DEG C and nitrogen
Under conditions of, preprepared LiO-(6-replaces-1-anthryl) is added dropwise to containing (indenyl) TiI3's
In THF solution so that LiO-(6-replaces-1-anthryl): (indenyl) TiI3Mol ratio be 1.1-1.3:1, mixed
Close liquid and slowly recover while room temperature to stir reaction 14-16h；
(2) cancellation: under ice-water bath, takes 1.5-2.5 times based on step (1) gained mixeding liquid volume full
And ammonium chloride solution, instill in step (1) gained mixed liquor slowly, reaction cancellation；
(3) extraction: by the ethyl acetate extraction step in three times of 3 times of volumes of step (2) gained reactant liquor
(2) gained solution, merges gained organic facies, is dried with anhydrous magnesium sulfate, is evaporated off molten at 50 DEG C of backspins
Agent, obtains crude product；
(4) recrystallization: crude product is dissolved by the ethanol of step (3) gained crude product stereometer 1 times,
Add the petroleum ether of crude product stereometer 4 times afterwards, the refrigerator-freezer of-30 DEG C carries out recrystallization, i.e. obtains cyclopentadienyl
Metallic compound；
(5) compounding: metallocene compound step (4) prepared and lithium chloride are 1-2:2-1 according to mol ratio
Ratio mixes, and in methanol, stirring reaction 1-2h, drains solvent subsequently under 0.8-1.2MPa and i.e. obtain product
Composite metallocene catalyst for norbornene polymerization.
3, as claimed in claim 2 for the composite metallocene catalyst of norbornene polymerization, it is characterized in that:
Substituent group in described LiO-(6-replaces-1-anthryl) is ethyl, propyl group, chloromethyl, isopropyl, chlorine, methyl
In one.
Beneficial effects of the present invention: the novel metallocene catalyst that the present invention uses is worked as in the polymerization of norborene
In have excellence catalysis activity, the molecular weight distribution obtained is narrow, and excellent performance promotes alkene
The development of polymerization industry.
Detailed description of the invention
Hereinafter, the present invention has been done specific experiment by applicant, and describes a class composite metallocene in detail and urge
Agent applies the experimentation in norbornene polymerization.These are only used for elaborating the present invention, not with
Any mode limits the scope of invention.
Embodiment 1
(1)(indenyl)TiI3Preparation:
A, first addition indenes (16mmol, 1.0eq.), 100mL THF in the round-bottomed flask of a 100mL；
Then the most dropwise drip butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) at-78 DEG C, be warmed to room temperature stirring
4h, adds trim,ethylchlorosilane (19.2mmol, 1.2eq.) afterwards at-78 DEG C, is warmed to room temperature and is stirred overnight,
Trimethyl silicane indenyl is obtained after reactant liquor decompression distillation.
B, at 0 DEG C in the dichloromethane (in advance except water) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reactant liquor is warmed to room temperature and continues stirring 5h, and reaction removes solvent after terminating, and adds the just own of 3:1
Alkane and dichloromethane solvent, twice of recrystallization, obtain sterling (indenyl) TiI3。
(2) preparation of metallocene compound:
Under-35 DEG C and condition of nitrogen gas, ready LiO-(6-ethyl-1-anthryl) is added dropwise to
(indenyl)TiI3THF solution in so that LiO-(6-replaces-1-anthryl): (indenyl) TiI3Mol ratio be
1.1:1, mixture slowly recovers to reaction 15h is stirred at room temperature.
The saturated ammonium chloride cancellation of 1 times of volume of gained mixture, 3 times of volume of ethylacetate extract in three times,
Merging organic facies, after 50 DEG C of rotations are evaporated off solvent, crude product uses the ethyl alcohol recrystallization of 1 times of volume to obtain cyclopentadienyl
Metallic compound, productivity: 72%.
It is (3) compounding: the metallocene compound obtained is mixed according to the ratio that mol ratio is 1:1 with lithium chloride,
Stirring 1 hour in methanol, reaction drains solvent after terminating, and i.e. obtains composite metallocene catalyst.
The polymerization of norborene: first Schlenk bottle is substituted ethylene twice, adds norborene (1.5mmol)
Xylene solution (20mL) in reactor, be slowly added to MAO (0.015mmol), room temperature afterwards
Add the composite metallocene catalyst of compounding substances gauge 0.05% after lower stirring 1 hour, be rapidly heated to
80 DEG C, keep ethylene pressure at 2atm, after continuing reaction 2.5 hours, stop stirring.Afterwards by reactant liquor
Join in the middle of ethanol, have white gum thing to generate, obtain norbornene polymer by washing with alcohol.
Recording polymer Mn through GPC is 427432, and Mn/Mw is 1.26.
Embodiment 2
(1)(indenyl)TiI3Preparation:
A, in the round-bottomed flask of a 100mL add indenes (16mmol, 1.0eq.), 100mL THF；Then
The most dropwise drip butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) at-78 DEG C, be warmed to room temperature stirring 4h,
At-78 DEG C, add trim,ethylchlorosilane (19.2mmol, 1.2eq.) afterwards, be warmed to room temperature and be stirred overnight, instead
Trimethyl silicane indenyl is obtained after answering liquid decompression distillation.
B, at 0 DEG C in the dichloromethane (in advance except water) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reactant liquor is warmed to room temperature continuation stirring 5h, and reaction removes solvent after terminating, adds the normal hexane of 3:1
With twice of dichloromethane solvent recrystallization, obtain sterling.
(2) preparation of metallocene compound:
Under-35 DEG C and condition of nitrogen gas, it is added dropwise over joining by ready LiO-(6-ethyl-1-anthryl)
(indenyl)TiI3THF solution in so that LiO-(6-replaces-1-anthryl): (indenyl) TiI3Mol ratio be
1.2:1, mixture slowly recovers to reaction 15h is stirred at room temperature；
The mixture obtained 1 times of saturated ammonium chloride cancellation, ethyl acetate extract, and merge organic facies, and rotation is steamed
After removing solvent, crude product uses ethyl alcohol recrystallization to obtain metallocene compound, productivity: 72%.
It is (3) compounding: the metallocene compound obtained is mixed according to the ratio that mol ratio is 1:2 with lithium chloride,
Stirring 1 hour in methanol, reaction drains solvent after terminating, and i.e. obtains composite metallocene catalyst.
The polymerization of norborene: first Schlenk bottle is substituted ethylene twice, adds norborene (1.5mmol)
Xylene solution (20mL) in reactor, be slowly added to MAO (0.015mmol), room temperature afterwards
Lower stirring added metallocene compound (by reactant liquor stereometer 0.05%) after 1 hour, was rapidly heated to 80
DEG C, keep ethylene pressure at 2atm, after continuing reaction 2.5 hours, stop stirring.Afterwards reactant liquor is added
Enter in the middle of ethanol, have white gum thing to generate, obtain norbornene polymer by washing with alcohol.
Recording polymer Mn through GPC is 427432, and Mn/Mw is 1.26.
Embodiment 3
(1)(indenyl)TiI3Preparation:
A, in the round-bottomed flask of a 100mL add indenes (16mmol, 1.0eq.), 100mL THF；So
The most dropwise drip butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) at-78 DEG C afterwards, be warmed to room temperature stirring 4
H, adds trim,ethylchlorosilane (19.2mmol, 1.2eq.) afterwards at-78 DEG C, is warmed to room temperature and is stirred overnight,
Trimethyl silicane indenyl is obtained after reactant liquor decompression distillation.
B, at 0 DEG C in the dichloromethane (in advance except water) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reactant liquor is warmed to room temperature and continues stirring 5h, and reaction removes solvent after terminating, and adds the just own of 3:1
Alkane and twice of dichloromethane solvent recrystallization, obtain sterling.
(2) preparation of metallocene compound:
Under-35 DEG C and condition of nitrogen gas, it is added dropwise over joining by ready LiO-(6-ethyl-1-anthryl)
(indenyl)TiI3THF solution in so that LiO-(6-replaces-1-anthryl): (indenyl) TiI3Mol ratio be
1.3:1, mixture slowly recovers to reaction 15h is stirred at room temperature；
The saturated ammonium chloride cancellation of gained mixture, ethyl acetate extracts, and merges organic facies, and rotation is evaporated off molten
After agent, crude product uses ethyl alcohol recrystallization to obtain metallocene compound, productivity: 72%.
It is (3) compounding: the metallocene compound obtained is mixed according to the ratio that mol ratio is 2:1 with lithium chloride,
Stirring 1 hour in methanol, reaction drains solvent after terminating, and i.e. obtains composite metallocene catalyst.
The polymerization of norborene: first Schlenk bottle is substituted ethylene twice, adds norborene (1.5mmol)
Xylene solution (20mL) in reactor, be slowly added to MAO (0.015mmol), room temperature afterwards
Lower stirring added metallocene compound (0.05%) after 1 hour, was rapidly heated to 80 DEG C, kept ethylene pressure
Power, at 2atm, stops stirring after continuing reaction 2.5 hours.Afterwards reactant liquor is joined in the middle of ethanol,
There is white gum thing to generate, obtain norbornene polymer by washing with alcohol.
Recording polymer Mn through GPC is 427432, and Mn/Mw is 1.26.
Embodiment 4
(1)(indenyl)TiI3Preparation:
A, in the round-bottomed flask of 100mL add indenes (16mmol, 1.0eq.), 100mL THF；Then-78
The most dropwise drip butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) at DEG C, be warmed to room temperature stirring 4h, it
After at-78 DEG C add trim,ethylchlorosilane (19.2mmol, 1.2eq.), be warmed to room temperature and be stirred overnight, reaction
Trimethyl silicane indenyl is obtained after liquid decompression distillation.
B, at 0 DEG C in the dichloromethane (in advance except water) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reactant liquor is warmed to room temperature and continues stirring 5h, and reaction removes solvent after terminating, and adds the just own of 3:1
Alkane and twice of dichloromethane solvent recrystallization, obtain sterling.
(2) preparation of metallocene compound:
Under-35 DEG C and condition of nitrogen gas, ready LiO-(6-chloromethyl-1-anthryl) is added dropwise to containing
(indenyl)TiI3THF solution in so that LiO-(6-replaces-1-anthryl): (indenyl) TiI3Mol ratio be
1.2:1, mixture slowly recovers to reaction 14h is stirred at room temperature；
The saturated ammonium chloride cancellation of gained mixture, ethyl acetate extracts, and merges organic facies, and 50 DEG C of backspins steam
After removing solvent, crude product uses ethyl alcohol recrystallization to obtain metallocene compound, productivity: 64%.
(3) metallocene compound obtained is mixed, in first according to the ratio that mol ratio is 1:1 with lithium chloride
Stirring 1 hour in alcohol, reaction drains solvent after terminating, and i.e. obtains composite metallocene catalyst.
The polymerization of norborene: first Schlenk bottle is substituted ethylene twice, adds norborene (1.5mmol)
Xylene solution (20mL) in reactor, be slowly added to MAO (0.015mmol), room temperature afterwards
Lower stirring added metallocene compound (by reactant liquor stereometer 0.05%) after 1 hour, was rapidly heated to 60
DEG C, keep ethylene pressure at 1atm, after continuing reaction stirring 2 hours, stop stirring.Afterwards by reactant liquor
Join in the middle of ethanol, have white gum thing to generate, obtain norbornene polymer by washing with alcohol.
Recording polymer Mn through GPC is 384460, and Mn/Mw is 1.29.
Embodiment 5
(1)(indenyl)TiI3Preparation:
A, in the round-bottomed flask of 100mL add indenes (16mmol, 1.0eq.), 100mL THF；Then-78
The most dropwise drip butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) at DEG C, be warmed to room temperature stirring 4h, it
After at-78 DEG C add trim,ethylchlorosilane (19.2mmol, 1.2eq.), be warmed to room temperature and be stirred overnight, reactant liquor
Trimethyl silicane indenyl is obtained after decompression distillation.
B, at 0 DEG C in the dichloromethane (in advance except water) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reactant liquor is warmed to room temperature and continues stirring 5h, and reaction removes solvent after terminating, and adds the just own of 3:1
Alkane and twice of dichloromethane solvent recrystallization, obtain sterling.
(2) preparation of metallocene compound:
Under-35 DEG C and condition of nitrogen gas, ready LiO-(6-chloromethyl-1-anthryl) is added dropwise to containing
(indenyl)TiI3THF solution in so that LiO-(6-replaces-1-anthryl): (indenyl) TiI3Mol ratio be
1.3:1, mixture slowly recovers to reaction 14h is stirred at room temperature；
The saturated ammonium chloride cancellation of gained mixture, ethyl acetate extracts, and merges organic facies, and rotation is evaporated off molten
After agent, crude product uses ethyl alcohol recrystallization to obtain metallocene compound, productivity: 64%.
It is (3) compounding: the metallocene compound obtained is mixed according to the ratio that mol ratio is 1:2 with lithium chloride,
Stirring 1 hour in methanol, reaction drains solvent after terminating, and i.e. obtains composite metallocene catalyst.
The polymerization of norborene: first Schlenk bottle is substituted ethylene twice, adds norborene (1.5mmol)
Xylene solution (20mL) in reactor, be slowly added to MAO (0.015mmol), room temperature afterwards
Lower stirring added metallocene compound (by reactant liquor stereometer 0.05%) after 1 hour, was rapidly heated to 60
DEG C, keep ethylene pressure at 1atm, after continuing reaction stirring 2 hours, stop stirring.Afterwards by reactant liquor
Join in the middle of ethanol, have white gum thing to generate, obtain norbornene polymer by washing with alcohol.
Recording polymer Mn through GPC is 384460, and Mn/Mw is 1.29.
Embodiment 6
(1)(indenyl)TiI3Preparation:
A, in the round-bottomed flask of 100mL add indenes (16mmol, 1.0eq.), 100mL THF；Then-78
The most dropwise drip butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) at DEG C, be warmed to room temperature stirring 4h,
At-78 DEG C, add trim,ethylchlorosilane (19.2mmol, 1.2eq.) afterwards, be warmed to room temperature and be stirred overnight, reaction
Trimethyl silicane indenyl is obtained after liquid decompression distillation.
B, at 0 DEG C in the dichloromethane (in advance except water) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reactant liquor is warmed to room temperature and continues stirring 5h, and reaction removes solvent after terminating, and adds the just own of 3:1
Alkane and twice of dichloromethane solvent recrystallization, obtain sterling.
(2) preparation of metallocene compound:
Under-35 DEG C and condition of nitrogen gas, ready LiO-(6-chloromethyl-1-anthryl) is added dropwise to containing
(indenyl)TiI3THF solution in so that LiO-(6-replaces-1-anthryl): (indenyl) TiI3Mol ratio be
1.1:1, mixture slowly recovers to reaction 14h is stirred at room temperature；
The saturated ammonium chloride cancellation of 1 times of volume of gained mixture, the ethyl acetate of 3 times of volumes extracts in three times,
Merging organic facies, after 50 DEG C of backspins are evaporated off solvent, crude product uses ethyl alcohol recrystallization to obtain metallocene chemical combination
Thing, productivity: 64%.
It is (3) compounding: the metallocene compound obtained is mixed according to the ratio that mol ratio is 2:1 with lithium chloride,
Stirring 1 hour in methanol, reaction drains solvent after terminating, and i.e. obtains composite metallocene catalyst.
The polymerization of norborene: first Schlenk bottle is substituted ethylene twice, adds norborene (1.5mmol)
Xylene solution (20mL) in reactor, be slowly added to MAO (0.015mmol), room temperature afterwards
Lower stirring added metallocene compound (by reactant liquor stereometer 0.05%) after 1 hour, was rapidly heated to 60
DEG C, keep ethylene pressure at 1atm, after continuing reaction stirring 2 hours, stop stirring.Afterwards by reactant liquor
Join in the middle of ethanol, have white gum thing to generate, obtain norbornene polymer by washing with alcohol.
Recording polymer Mn through GPC is 384460, and Mn/Mw is 1.29.
Embodiment 7
(1)(indenyl)TiI3Preparation:
A, in the round-bottomed flask of 100mL add indenes (16mmol, 1.0eq.), 100mL THF；Then-78
The most dropwise drip butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) at DEG C, be warmed to room temperature stirring 4h,
At-78 DEG C, add trim,ethylchlorosilane (19.2mmol, 1.2eq.) afterwards, be warmed to room temperature and be stirred overnight, reaction
Trimethyl silicane indenyl is obtained after liquid decompression distillation.
B, at 0 DEG C in the dichloromethane (in advance except water) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reactant liquor is warmed to room temperature continuation stirring 5h, and reaction removes solvent after terminating, adds the normal hexane of 3:1
With twice of dichloromethane solvent recrystallization, obtain sterling.
(2) preparation of metallocene compound:
Under-35 DEG C and condition of nitrogen gas, ready LiO-(6-propyl group-1-anthryl) is added dropwise to containing
(indenyl)TiI3THF solution in so that LiO-(6-replaces-1-anthryl): (indenyl) TiI3Mol ratio be
1.3:1, mixture slowly recovers to reaction 12h is stirred at room temperature；
The saturated ammonium chloride cancellation of 1 times of volume of gained mixture, the ethyl acetate extraction of 3 times of volumes, merge
Organic facies, after 50 DEG C of backspins are evaporated off solvent, crude product uses ethyl alcohol recrystallization to obtain metallocene compound,
Productivity: 61%.
It is (3) compounding: the metallocene compound obtained is mixed according to the ratio that mol ratio is 1:1 with lithium chloride,
Stirring 1 hour in methanol, reaction drains solvent after terminating, and i.e. obtains composite metallocene catalyst.
The polymerization of norborene: first Schlenk bottle is substituted ethylene twice, adds norborene (1.5mmol)
Xylene solution (30mL) in reactor, be slowly added to MAO (0.015mmol), room temperature afterwards
Lower stirring added metallocene compound (by reactant liquor stereometer 0.05%) after 1 hour, was rapidly heated to 50
DEG C, keep ethylene pressure at 3atm, after continuing reaction 4 hours, stop stirring.Afterwards reactant liquor is added
In the middle of ethanol, there is white gum thing to generate, obtain norbornene polymer by washing with alcohol.
Recording polymer Mn through GPC is 330805, and Mn/Mw is 1.25.
Embodiment 8
(1)(indenyl)TiI3Preparation:
A, in the round-bottomed flask of 100mL add indenes (16mmol, 1.0eq.), 100mL THF；Then-78
The most dropwise drip butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) at DEG C, be warmed to room temperature stirring 4h, it
After at-78 DEG C add trim,ethylchlorosilane (19.2mmol, 1.2eq.), be warmed to room temperature and be stirred overnight, reaction
Trimethyl silicane indenyl is obtained after liquid decompression distillation.
B, at 0 DEG C in the dichloromethane (in advance except water) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reactant liquor is warmed to room temperature and continues stirring 5h, and reaction removes solvent after terminating, and adds the just own of 3:1
Alkane and twice of dichloromethane solvent recrystallization, obtain sterling.
(2) preparation of metallocene compound:
Under-35 DEG C and condition of nitrogen gas, ready LiO-(6-propyl group-1-anthryl) is added dropwise to containing
(indenyl)TiI3THF solution in so that LiO-(6-replaces-1-anthryl): (indenyl) TiI3Mol ratio be
1.2:1, mixture slowly recovers to reaction 12h is stirred at room temperature；
The saturated ammonium chloride cancellation of 1 times of volume of gained mixture, the ethyl acetate of 3 times of volumes extracts in three times,
Merging organic facies, after 50 DEG C of backspins are evaporated off solvent, crude product uses ethyl alcohol recrystallization to obtain metallocene chemical combination
Thing, productivity: 61%.
It is (3) compounding: the metallocene compound obtained is mixed according to the ratio that mol ratio is 1:2 with lithium chloride,
Stirring 1 hour in methanol, reaction drains solvent after terminating, and i.e. obtains composite metallocene catalyst.
The polymerization of norborene: first Schlenk bottle is substituted ethylene twice, adds norborene (1.5mmol)
Xylene solution (30mL) in reactor, be slowly added to MAO (0.015mmol), room temperature afterwards
Lower stirring added metallocene compound (by reactant liquor stereometer 0.05%) after 1 hour, was rapidly heated to 50
DEG C, keep ethylene pressure at 3atm, after continuing reaction 4 hours, stop stirring.Afterwards reactant liquor is added
In the middle of ethanol, there is white gum thing to generate, obtain norbornene polymer by washing with alcohol.Record through GPC
Polymer Mn is 330805, and Mn/Mw is 1.25.
Embodiment 9
(1)(indenyl)TiI3Preparation:
A, in the round-bottomed flask of 100mL add indenes (16mmol, 1.0eq.), 100mL THF；Then-78
The most dropwise drip butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) at DEG C, be warmed to room temperature stirring 4h, it
After at-78 DEG C add trim,ethylchlorosilane (19.2mmol, 1.2eq.), be warmed to room temperature and be stirred overnight, reaction
Trimethyl silicane indenyl is obtained after liquid decompression distillation.
B, at 0 DEG C in the dichloromethane (in advance except water) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reactant liquor is warmed to room temperature and continues stirring 5h, and reaction removes solvent after terminating, and adds the just own of 3:1
Alkane and twice of dichloromethane solvent recrystallization, obtain sterling.
(2) preparation of metallocene catalyst:
Under-35 DEG C and condition of nitrogen gas, ready LiO-(6-propyl group-1-anthryl) is added dropwise to containing
(indenyl)TiI3THF solution in so that LiO-(6-replaces-1-anthryl): (indenyl) TiI3Mol ratio be
1.2:1, mixture slowly recovers to reaction 12h is stirred at room temperature；
The saturated ammonium chloride cancellation of 1 times of volume of gained mixture, the ethyl acetate of 3 times of volumes extracts in three times,
Merging organic facies, after 50 DEG C of backspins are evaporated off solvent, crude product uses ethyl alcohol recrystallization to obtain metallocene chemical combination
Thing, productivity: 61%.
It is (3) compounding: the metallocene compound obtained is mixed according to the ratio that mol ratio is 2:1 with lithium chloride,
Stirring 1 hour in methanol, reaction drains solvent after terminating, and i.e. obtains composite metallocene catalyst.
The polymerization of norborene: first Schlenk bottle is substituted ethylene twice, adds norborene (1.5mmol)
Xylene solution (30mL) in reactor, be slowly added to MAO (0.015mmol), room temperature afterwards
Lower stirring added metallocene compound (by reactant liquor stereometer 0.05%) after 1 hour, was rapidly heated to 50
DEG C, keep ethylene pressure at 3atm, after continuing reaction 4 hours, stop stirring.Afterwards reactant liquor is added
In the middle of ethanol, there is white gum thing to generate, obtain norbornene polymer by washing with alcohol.Record through GPC
Polymer Mn is 330805, and Mn/Mw is 1.25.
Claims (3)
1., for a composite metallocene catalyst for norbornene polymerization, it is characterized in that: with metallocene chemical combination
Thing is nucleus, metallocene compound and lithium chloride compound according to the mol ratio of 1-2:2-1；
The concrete structure of described wherein metallocene compound is as follows:
Wherein R=Me, Et or Cl.
2. the preparation method of the composite metallocene catalyst for norbornene polymerization described in claim 1,
Carry out as follows:
(1) reaction: take (indenyl) TiI3It is dissolved in THF solution ,-35 DEG C and the condition of nitrogen protection
Under, preprepared LiO-(6-replaces-1-anthryl) is added dropwise to containing (indenyl) TiI3THF molten
In liquid so that LiO-(6-replaces-1-anthryl): (indenyl) TiI3Mol ratio be 1.1-1.3:1, mixed liquor delay
Slow recovery stirs reaction 14-16h while room temperature；
(2) cancellation: under ice-water bath, takes 1.5-2.5 times based on step (1) gained mixeding liquid volume full
And ammonium chloride solution, instill in step (1) gained mixed liquor slowly, reaction cancellation；
(3) extraction: by the ethyl acetate extraction step in three times of 3 times of volumes of step (2) gained reactant liquor
(2) gained solution, merges gained organic facies, is dried with anhydrous magnesium sulfate, is evaporated off molten at 50 DEG C of backspins
Agent, obtains crude product；
(4) recrystallization: crude product is dissolved by the ethanol of step (3) gained crude product stereometer 1 times,
Add the petroleum ether of crude product stereometer 4 times afterwards, the refrigerator-freezer of-30 DEG C carries out recrystallization, i.e. obtains cyclopentadienyl
Metallic compound；
(5) compounding: metallocene compound step (4) prepared and lithium chloride are 1-2:2-1 according to mol ratio
Ratio mixes, and in methanol, stirring reaction 1-2h, drains solvent subsequently under 0.8-1.2MPa and i.e. obtain product
Composite metallocene catalyst for norbornene polymerization.
3. it is used for the preparation method of the composite metallocene catalyst of norbornene polymerization as claimed in claim 2,
It is characterized in that: the substituent group in described LiO-(6-replaces-1-anthryl) be ethyl, propyl group, chloromethyl, isopropyl,
One in chlorine or methyl.
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| CN1301272A (en) * | 1998-02-07 | 2001-06-27 | 巴塞尔聚丙烯股份有限公司 | Catalyst system |
| US20130035442A1 (en) * | 2011-08-04 | 2013-02-07 | Exxonmobil Research And Engineering Company | Elastic propylene-alpha-olefin copolymer compositions and processes to produce them |
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| US20130035442A1 (en) * | 2011-08-04 | 2013-02-07 | Exxonmobil Research And Engineering Company | Elastic propylene-alpha-olefin copolymer compositions and processes to produce them |
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