CN106008766B - A kind of composite metallocene catalyst for norbornene polymerization and preparation method thereof - Google Patents
A kind of composite metallocene catalyst for norbornene polymerization and preparation method thereof Download PDFInfo
- Publication number
- CN106008766B CN106008766B CN201610495924.2A CN201610495924A CN106008766B CN 106008766 B CN106008766 B CN 106008766B CN 201610495924 A CN201610495924 A CN 201610495924A CN 106008766 B CN106008766 B CN 106008766B
- Authority
- CN
- China
- Prior art keywords
- indenyl
- norbornene
- metallocene compound
- reaction
- tii
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- 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
-
- 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
-
- 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
- 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
- C08F232/08—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 having condensed rings
-
- 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
- C08F2420/00—Metallocene catalysts
- C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a kind of composite metallocene catalyst for norbornene polymerization and preparation method thereof, belong to polymeric material preparing technical field.It is using metallocene compound as nucleus, by metallocene compound and lithium chloride according to 12:21 molar ratio compounding.Composite metallocene catalyst catalyst synthesis processes prepared by the present invention are simple, and product extraction is easy after synthesis, and catalyst purification rate is high, can be reused by the method for recrystallization.Meanwhile catalyst provided by the invention shows excellent catalytic activity in the polymerization of norbornene, obtained polymer molecular weight narrowly distributing, excellent performance, has higher actual application prospect.
Description
Technical field
The present invention relates to a kind of composite metallocene catalyst for norbornene polymerization and preparation method thereof, belong to polymerization
Technical field of material.
Background technology
Metallocene catalyst and traditional catalyst it is maximum difference lies in：Metallocene catalyst only has an activated centre,
In the environment of its metallic atom is generally all in being restricted, only polymer monomer is allowed to enter on catalyst activity point.Therefore
Being capable of accurate control relative molar mass, relative molar mass distribution, co-monomer content and its distribution on main chain and clean
Net structure etc..Its polymer is a kind of polymer of high stereoregularity, and molecular weight distribution is extremely narrow.
The feature of metallocene catalyst single active center, can make any polymerizing olefin monomers, it is possible to achieve past solid is urged
The polymerization or copolyreaction of agent cannot polymerize or catalytic efficiency is extremely low cycloolefin, conjugated diene and polar monomer, so that
More high performance synthetic materials can be developed.Another feature of metallocene catalyst, is to accurately control polymerization process, makes it
Energy continuous production structure and the uniform polymer of performance, can be by user's requirement deisgn product performance.
Norbornene polymer is a kind of polymer of excellent performance, is widely used in multiple fields, in modern industry
There is larger application especially in terms of coating material, protection and its film forming.In recent years, China had started to gather norbornene
Conjunction is studied, and is flourished in the whole nation so far, except norbornene, the polymerization of some norbornene derivatives is also quick
In development, to meet industrially the needs of to such material.However, with the industrially requirement to norbornene polymer performance
Higher and higher, the polymerization product that different metallocenes obtains has very big performance difference, and most of performance is difficult to meet people
Demand, it is therefore desirable to develop the more excellent product of performance.
The content of the invention
It is an object of the present invention to overcome the above deficiencies, there is provided a kind of composite metallocene for norbornene polymerization
Catalyst and preparation method thereof.
According to technical solution provided by the invention, a kind of composite metallocene catalyst for norbornene polymerization, its with
Metallocene compound is nucleus, by metallocene compound and lithium chloride according to 1-2:The molar ratio compounding of 2-1.
The concrete structure of the wherein metallocene compound is as follows：
Wherein R=Me, Et or Cl.
The preparation method of the composite metallocene catalyst for norbornene polymerization, carries out as follows：
(1) react：Take (indenyl) TiI3It is dissolved in excessive THF solution, in -35 DEG C and the condition of nitrogen protection
Under, preprepared LiO- (6- substitutes -1- anthryls) is added dropwise to containing (indenyl) TiI3THF solution in, make
Obtain LiO- (6- substitution -1- anthryls)：(indenyl)TiI3Molar ratio be 1.1-1.3：1, mixed liquor slowly recovers to room temperature
Reaction 14-16h is stirred at the same time；
(2) it is quenched：Under ice-water bath, take 1.5-2.5 times based on mixeding liquid volume obtained by step (1) of saturated ammonium chloride molten
Liquid, slowly instills in mixed liquor obtained by step (1), reaction is quenched；
(3) extract：Extraction step (2) gained is molten in three times for the ethyl acetate of 3 times of volumes of reaction solution obtained by step (2)
Liquid, gained organic phase is merged, is dried with anhydrous magnesium sulfate, and solvent is evaporated off in 50 DEG C of backspins, obtains crude product；
(4) recrystallize：Crude product is dissolved by the ethanol of 1 times of crude product stereometer obtained by step (3), adds thick production afterwards
The petroleum ether that 4 times of volume, is recrystallized in -30 DEG C of refrigerator-freezer, that is, obtains metallocene compound；
(5) compound：According to molar ratio it is 1-2 by metallocene compound made from step (4) and lithium chloride:2-1 ratios are mixed
Close, in methyl alcohol stirring reaction 1-2h, solvent is then drained under 0.8-1.2MPa obtain product and be used for norbornene polymerization
Composite metallocene catalyst.
3rd, it is used for the composite metallocene catalyst of norbornene polymerization as claimed in claim 2, it is characterized in that：The LiO-
Substituent in (6- substitution -1- anthryls) is ethyl, one kind in propyl group, chloromethyl, isopropyl, chlorine, methyl.
Beneficial effects of the present invention：The new metallocene catalyst that the present invention uses has among the polymerization of norbornene
Excellent catalytic activity, obtained polymer molecular weight narrowly distributing, excellent performance, promotes the development of olefinic polymerization industry.
Embodiment
Hereinafter, applicant has been the present invention specific experiment, and a kind of composite metallocene catalyst is described in detail and answers
Experimentation in norbornene polymerization.These are only used for elaborating the present invention, not limitation invention in any way
Scope.
Embodiment 1
(1)(indenyl)TiI3Preparation：
A, indenes (16mmol, 1.0eq.), 100mL THF are added first into the round-bottomed flask of a 100mL；Then -78
Butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) is added dropwise at DEG C dropwise thereto, stirring 4h is warmed to room temperature, afterwards at -78 DEG C
Trim,ethylchlorosilane (19.2mmol, 1.2eq.) is added, is warmed to room temperature and is stirred overnight, trimethyl is obtained after reaction solution vacuum distillation
Silicon indenyl.
B, at 0 DEG C into the dichloromethane (in advance water removal) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reaction solution, which is warmed to room temperature, to be continued to stir 5h, is removed solvent after reaction, is added 3:1 n-hexane and dichloromethane
Alkane solvents, recrystallization twice, obtain sterling (indenyl) TiI3。
(2) preparation of metallocene compound：
Under -35 DEG C and condition of nitrogen gas, ready LiO- (6- ethyl -1- anthryls) is added dropwise to (indenyl)
TiI3THF solution in so that LiO- (6- substitution -1- anthryls)：(indenyl)TiI3Molar ratio be 1.1：1, mixture delays
It is slow to recover to reaction 15h is stirred at room temperature.
Gained mixture is quenched with the saturated ammonium chloride of 1 times of volume, and 3 times of volume of ethylacetate extract in three times, are associated with
Machine phase, after 50 DEG C of revolvings remove solvent, crude product obtains metallocene compound, yield using the ethyl alcohol recrystallization of 1 times of volume：
72%.
(3) compound：According to molar ratio it is 1 by obtained metallocene compound and lithium chloride:1 ratio mixing, in methanol
It is middle stirring 1 it is small when, drain solvent after reaction, that is, obtain composite metallocene catalyst.
The polymerization of norbornene：Ethene is substituted by Schlenk bottles twice, add the two of norbornene (1.5mmol) first
Toluene solution (20mL) is slowly added to methylaluminoxane (0.015mmol) afterwards in reactor, stirs 1 hour at room temperature
The composite metallocene catalyst of compounding substances gauge 0.05% is added afterwards, is rapidly heated to 80 DEG C, keeps ethylene pressure in 2atm,
Stop stirring after the reaction was continued 2.5 hours.Reaction solution is added among ethanol afterwards, has the generation of white gum thing, uses second
Alcohol washs to obtain norbornene polymer.
It is 427432, Mn/Mw 1.26 to measure polymer Mn through GPC.
Embodiment 2
(1)(indenyl)TiI3Preparation：
A, indenes (16mmol, 1.0eq.), 100mL THF are added into the round-bottomed flask of a 100mL；Then at -78 DEG C
Butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) is added dropwise dropwise thereto, is warmed to room temperature stirring 4h, is added afterwards at -78 DEG C
Trim,ethylchlorosilane (19.2mmol, 1.2eq.), is warmed to room temperature and is stirred overnight, and trimethyl silicane indenes is obtained after reaction solution vacuum distillation
Base.
B, at 0 DEG C into the dichloromethane (in advance water removal) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reaction solution, which is warmed to room temperature, to be continued to stir 5h, is removed solvent after reaction, is added 3:1 n-hexane and dichloromethane
Alkane solvents recrystallize twice, obtain sterling.
(2) preparation of metallocene compound：
Under -35 DEG C and condition of nitrogen gas, ready LiO- (6- ethyl -1- anthryls) is added dropwise and is added to
(indenyl)TiI3THF solution in so that LiO- (6- substitution -1- anthryls)：(indenyl)TiI3Molar ratio be 1.2：1,
Mixture slowly recover to be stirred at room temperature reaction 15h；
Obtained mixture is quenched with 1 times of saturated ammonium chloride, ethyl acetate extraction, merges organic phase, and revolving removes solvent
Afterwards, crude product obtains metallocene compound, yield using ethyl alcohol recrystallization：72%.
(3) compound：According to molar ratio it is 1 by obtained metallocene compound and lithium chloride:2 ratio mixing, in methanol
It is middle stirring 1 it is small when, drain solvent after reaction, that is, obtain composite metallocene catalyst.
The polymerization of norbornene：Ethene is substituted by Schlenk bottles twice, add the two of norbornene (1.5mmol) first
Toluene solution (20mL) is slowly added to methylaluminoxane (0.015mmol) afterwards in reactor, stirs 1 hour at room temperature
Add metallocene compound (press reaction solution stereometer 0.05%) afterwards, be rapidly heated to 80 DEG C, holding ethylene pressure in 2atm, after
Stop stirring after 2.5 hours of continuous reaction.Reaction solution is added among ethanol afterwards, has the generation of white gum thing, uses ethanol
Wash to obtain norbornene polymer.
It is 427432, Mn/Mw 1.26 to measure polymer Mn through GPC.
Embodiment 3
(1)(indenyl)TiI3Preparation：
A, indenes (16mmol, 1.0eq.), 100mL THF are added into the round-bottomed flask of a 100mL；Then at -78 DEG C
Butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) is added dropwise dropwise thereto, is warmed to room temperature stirring 4h, is added afterwards at -78 DEG C
Trim,ethylchlorosilane (19.2mmol, 1.2eq.), is warmed to room temperature and is stirred overnight, and trimethyl silicane indenes is obtained after reaction solution vacuum distillation
Base.
B, at 0 DEG C into the dichloromethane (in advance water removal) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reaction solution, which is warmed to room temperature, to be continued to stir 5h, is removed solvent after reaction, is added 3:1 n-hexane and dichloromethane
Alkane solvents recrystallize twice, obtain sterling.
(2) preparation of metallocene compound：
Under -35 DEG C and condition of nitrogen gas, ready LiO- (6- ethyl -1- anthryls) is added dropwise and is added to
(indenyl)TiI3THF solution in so that LiO- (6- substitution -1- anthryls)：(indenyl)TiI3Molar ratio be 1.3：1,
Mixture slowly recover to be stirred at room temperature reaction 15h；
Gained mixture is quenched with saturated ammonium chloride, and ethyl acetate extraction, merges organic phase, after revolving removes solvent, slightly
Product obtains metallocene compound, yield using ethyl alcohol recrystallization：72%.
(3) compound：According to molar ratio it is 2 by obtained metallocene compound and lithium chloride:1 ratio mixing, in methanol
It is middle stirring 1 it is small when, drain solvent after reaction, that is, obtain composite metallocene catalyst.
The polymerization of norbornene：Ethene is substituted by Schlenk bottles twice, add the two of norbornene (1.5mmol) first
Toluene solution (20mL) is slowly added to methylaluminoxane (0.015mmol) afterwards in reactor, stirs 1 hour at room temperature
Metallocene compound (0.05%) is added afterwards, is rapidly heated to 80 DEG C, and keeping ethylene pressure, it is 2.5 small that the reaction was continued in 2atm
When after stop stirring.Reaction solution is added among ethanol afterwards, has the generation of white gum thing, norbornene is washed to obtain with ethanol
Polymer.
It is 427432, Mn/Mw 1.26 to measure polymer Mn through GPC.
Embodiment 4
(1)(indenyl)TiI3Preparation：
A, indenes (16mmol, 1.0eq.), 100mL THF are added into the round-bottomed flask of 100mL；Then to it at -78 DEG C
In butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) is added dropwise dropwise, be warmed to room temperature stirring 4h, add front three at -78 DEG C afterwards
Base chlorosilane (19.2mmol, 1.2eq.), is warmed to room temperature and is stirred overnight, and trimethyl silicane indenyl is obtained after reaction solution vacuum distillation.
B, at 0 DEG C into the dichloromethane (in advance water removal) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reaction solution, which is warmed to room temperature, to be continued to stir 5h, is removed solvent after reaction, is added 3:1 n-hexane and dichloromethane
Alkane solvents recrystallize twice, obtain sterling.
(2) preparation of metallocene compound：
Under -35 DEG C and condition of nitrogen gas, by ready LiO- (6- chloromethyl -1- anthryls) be added dropwise to containing
(indenyl)TiI3THF solution in so that LiO- (6- substitution -1- anthryls)：(indenyl)TiI3Molar ratio be 1.2：1,
Mixture slowly recover to be stirred at room temperature reaction 14h；
Gained mixture is quenched with saturated ammonium chloride, and ethyl acetate extraction, merges organic phase, solvent is evaporated off in 50 DEG C of backspins
Afterwards, crude product obtains metallocene compound, yield using ethyl alcohol recrystallization：64%.
(3) it is 1 according to molar ratio by obtained metallocene compound and lithium chloride:1 ratio mixing, is stirred in methyl alcohol
1 it is small when, drain solvent after reaction, that is, obtain composite metallocene catalyst.
The polymerization of norbornene：Ethene is substituted by Schlenk bottles twice, add the two of norbornene (1.5mmol) first
Toluene solution (20mL) is slowly added to methylaluminoxane (0.015mmol) afterwards in reactor, stirs 1 hour at room temperature
Add metallocene compound (press reaction solution stereometer 0.05%) afterwards, be rapidly heated to 60 DEG C, holding ethylene pressure in 1atm, after
Stop stirring after continuous reaction 2 hours of stirring.Reaction solution is added among ethanol afterwards, has the generation of white gum thing, uses second
Alcohol washs to obtain norbornene polymer.
It is 384460, Mn/Mw 1.29 to measure polymer Mn through GPC.
Embodiment 5
(1)(indenyl)TiI3Preparation：
A, indenes (16mmol, 1.0eq.), 100mL THF are added into the round-bottomed flask of 100mL；Then to it at -78 DEG C
In butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) is added dropwise dropwise, be warmed to room temperature stirring 4h, add front three at -78 DEG C afterwards
Base chlorosilane (19.2mmol, 1.2eq.), is warmed to room temperature and is stirred overnight, and trimethyl silicane indenyl is obtained after reaction solution vacuum distillation.
B, at 0 DEG C into the dichloromethane (in advance water removal) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reaction solution, which is warmed to room temperature, to be continued to stir 5h, is removed solvent after reaction, is added 3:1 n-hexane and dichloromethane
Alkane solvents recrystallize twice, obtain sterling.
(2) preparation of metallocene compound：
Under -35 DEG C and condition of nitrogen gas, by ready LiO- (6- chloromethyl -1- anthryls) be added dropwise to containing
(indenyl)TiI3THF solution in so that LiO- (6- substitution -1- anthryls)：(indenyl)TiI3Molar ratio be 1.3：1,
Mixture slowly recover to be stirred at room temperature reaction 14h；
Gained mixture is quenched with saturated ammonium chloride, and ethyl acetate extraction, merges organic phase, after revolving removes solvent, slightly
Product obtains metallocene compound, yield using ethyl alcohol recrystallization：64%.
(3) compound：According to molar ratio it is 1 by obtained metallocene compound and lithium chloride:2 ratio mixing, in methanol
It is middle stirring 1 it is small when, drain solvent after reaction, that is, obtain composite metallocene catalyst.
The polymerization of norbornene：Ethene is substituted by Schlenk bottles twice, add the two of norbornene (1.5mmol) first
Toluene solution (20mL) is slowly added to methylaluminoxane (0.015mmol) afterwards in reactor, stirs 1 hour at room temperature
Add metallocene compound (press reaction solution stereometer 0.05%) afterwards, be rapidly heated to 60 DEG C, holding ethylene pressure in 1atm, after
Stop stirring after continuous reaction 2 hours of stirring.Reaction solution is added among ethanol afterwards, has the generation of white gum thing, uses second
Alcohol washs to obtain norbornene polymer.
It is 384460, Mn/Mw 1.29 to measure polymer Mn through GPC.
Embodiment 6
(1)(indenyl)TiI3Preparation：
A, indenes (16mmol, 1.0eq.), 100mL THF are added into the round-bottomed flask of 100mL；Then to it at -78 DEG C
In butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) is added dropwise dropwise, be warmed to room temperature stirring 4h, add front three at -78 DEG C afterwards
Base chlorosilane (19.2mmol, 1.2eq.), is warmed to room temperature and is stirred overnight, and trimethyl silicane indenyl is obtained after reaction solution vacuum distillation.
B, at 0 DEG C into the dichloromethane (in advance water removal) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reaction solution, which is warmed to room temperature, to be continued to stir 5h, is removed solvent after reaction, is added 3:1 n-hexane and dichloromethane
Alkane solvents recrystallize twice, obtain sterling.
(2) preparation of metallocene compound：
Under -35 DEG C and condition of nitrogen gas, by ready LiO- (6- chloromethyl -1- anthryls) be added dropwise to containing
(indenyl)TiI3THF solution in so that LiO- (6- substitution -1- anthryls)：(indenyl)TiI3Molar ratio be 1.1：1,
Mixture slowly recover to be stirred at room temperature reaction 14h；
Gained mixture is quenched with the saturated ammonium chloride of 1 times of volume, and the ethyl acetate of 3 times of volumes extracts in three times, is merged
Organic phase, after solvent is evaporated off in 50 DEG C of backspins, crude product obtains metallocene compound, yield using ethyl alcohol recrystallization：64%.
(3) compound：According to molar ratio it is 2 by obtained metallocene compound and lithium chloride:1 ratio mixing, in methanol
It is middle stirring 1 it is small when, drain solvent after reaction, that is, obtain composite metallocene catalyst.
The polymerization of norbornene：Ethene is substituted by Schlenk bottles twice, add the two of norbornene (1.5mmol) first
Toluene solution (20mL) is slowly added to methylaluminoxane (0.015mmol) afterwards in reactor, stirs 1 hour at room temperature
Add metallocene compound (press reaction solution stereometer 0.05%) afterwards, be rapidly heated to 60 DEG C, holding ethylene pressure in 1atm, after
Stop stirring after continuous reaction 2 hours of stirring.Reaction solution is added among ethanol afterwards, has the generation of white gum thing, uses second
Alcohol washs to obtain norbornene polymer.
It is 384460, Mn/Mw 1.29 to measure polymer Mn through GPC.
Embodiment 7
(1)(indenyl)TiI3Preparation：
A, indenes (16mmol, 1.0eq.), 100mL THF are added into the round-bottomed flask of 100mL；Then to it at -78 DEG C
In butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) is added dropwise dropwise, be warmed to room temperature stirring 4h, add front three at -78 DEG C afterwards
Base chlorosilane (19.2mmol, 1.2eq.), is warmed to room temperature and is stirred overnight, and trimethyl silicane indenyl is obtained after reaction solution vacuum distillation.
B, at 0 DEG C into the dichloromethane (in advance water removal) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reaction solution, which is warmed to room temperature, to be continued to stir 5h, is removed solvent after reaction, is added 3:1 n-hexane and dichloromethane
Alkane solvents recrystallize twice, obtain sterling.
(2) preparation of metallocene compound：
Under -35 DEG C and condition of nitrogen gas, by ready LiO- (6- propyl group -1- anthryls) be added dropwise to containing
(indenyl)TiI3THF solution in so that LiO- (6- substitution -1- anthryls)：(indenyl)TiI3Molar ratio be 1.3：1,
Mixture slowly recover to be stirred at room temperature reaction 12h；
Gained mixture is quenched with the saturated ammonium chloride of 1 times of volume, and the ethyl acetate extraction of 3 times of volumes, merges organic phase,
After solvent is evaporated off in 50 DEG C of backspins, crude product obtains metallocene compound, yield using ethyl alcohol recrystallization：61%.
(3) compound：According to molar ratio it is 1 by obtained metallocene compound and lithium chloride:1 ratio mixing, in methanol
It is middle stirring 1 it is small when, drain solvent after reaction, that is, obtain composite metallocene catalyst.
The polymerization of norbornene：Ethene is substituted by Schlenk bottles twice, add the two of norbornene (1.5mmol) first
Toluene solution (30mL) is slowly added to methylaluminoxane (0.015mmol) afterwards in reactor, stirs 1 hour at room temperature
Add metallocene compound (press reaction solution stereometer 0.05%) afterwards, be rapidly heated to 50 DEG C, holding ethylene pressure in 3atm, after
Stop stirring after 4 hours of continuous reaction.Reaction solution is added among ethanol afterwards, has the generation of white gum thing, is washed with ethanol
Wash to obtain norbornene polymer.
It is 330805, Mn/Mw 1.25 to measure polymer Mn through GPC.
Embodiment 8
(1)(indenyl)TiI3Preparation：
A, indenes (16mmol, 1.0eq.), 100mL THF are added into the round-bottomed flask of 100mL；Then to it at -78 DEG C
In butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) is added dropwise dropwise, be warmed to room temperature stirring 4h, add front three at -78 DEG C afterwards
Base chlorosilane (19.2mmol, 1.2eq.), is warmed to room temperature and is stirred overnight, and trimethyl silicane indenyl is obtained after reaction solution vacuum distillation.
B, at 0 DEG C into the dichloromethane (in advance water removal) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reaction solution, which is warmed to room temperature, to be continued to stir 5h, is removed solvent after reaction, is added 3:1 n-hexane and dichloromethane
Alkane solvents recrystallize twice, obtain sterling.
(2) preparation of metallocene compound：
Under -35 DEG C and condition of nitrogen gas, by ready LiO- (6- propyl group -1- anthryls) be added dropwise to containing
(indenyl)TiI3THF solution in so that LiO- (6- substitution -1- anthryls)：(indenyl)TiI3Molar ratio be 1.2：1,
Mixture slowly recover to be stirred at room temperature reaction 12h；
Gained mixture is quenched with the saturated ammonium chloride of 1 times of volume, and the ethyl acetate of 3 times of volumes extracts in three times, is merged
Organic phase, after solvent is evaporated off in 50 DEG C of backspins, crude product obtains metallocene compound, yield using ethyl alcohol recrystallization：61%.
(3) compound：According to molar ratio it is 1 by obtained metallocene compound and lithium chloride:2 ratio mixing, in methanol
It is middle stirring 1 it is small when, drain solvent after reaction, that is, obtain composite metallocene catalyst.
The polymerization of norbornene：Ethene is substituted by Schlenk bottles twice, add the two of norbornene (1.5mmol) first
Toluene solution (30mL) is slowly added to methylaluminoxane (0.015mmol) afterwards in reactor, stirs 1 hour at room temperature
Add metallocene compound (press reaction solution stereometer 0.05%) afterwards, be rapidly heated to 50 DEG C, holding ethylene pressure in 3atm, after
Stop stirring after 4 hours of continuous reaction.Reaction solution is added among ethanol afterwards, has the generation of white gum thing, is washed with ethanol
Wash to obtain norbornene polymer.It is 330805, Mn/Mw 1.25 to measure polymer Mn through GPC.
Embodiment 9
(1)(indenyl)TiI3Preparation：
A, indenes (16mmol, 1.0eq.), 100mL THF are added into the round-bottomed flask of 100mL；Then to it at -78 DEG C
In butyl lithium (1.6M/L, 17.6mmol, 1.1eq.) is added dropwise dropwise, be warmed to room temperature stirring 4h, add front three at -78 DEG C afterwards
Base chlorosilane (19.2mmol, 1.2eq.), is warmed to room temperature and is stirred overnight, and trimethyl silicane indenyl is obtained after reaction solution vacuum distillation.
B, at 0 DEG C into the dichloromethane (in advance water removal) of trimethyl silicane indenyl (1.0eq.) by titanium tetra iodide
(1.2eq.), reaction solution, which is warmed to room temperature, to be continued to stir 5h, is removed solvent after reaction, is added 3:1 n-hexane and dichloromethane
Alkane solvents recrystallize twice, obtain sterling.
(2) preparation of metallocene catalyst：
Under -35 DEG C and condition of nitrogen gas, by ready LiO- (6- propyl group -1- anthryls) be added dropwise to containing
(indenyl)TiI3THF solution in so that LiO- (6- substitution -1- anthryls)：(indenyl)TiI3Molar ratio be 1.2：1,
Mixture slowly recover to be stirred at room temperature reaction 12h；
Gained mixture is quenched with the saturated ammonium chloride of 1 times of volume, and the ethyl acetate of 3 times of volumes extracts in three times, is merged
Organic phase, after solvent is evaporated off in 50 DEG C of backspins, crude product obtains metallocene compound, yield using ethyl alcohol recrystallization：61%.
(3) compound：According to molar ratio it is 2 by obtained metallocene compound and lithium chloride:1 ratio mixing, in methanol
It is middle stirring 1 it is small when, drain solvent after reaction, that is, obtain composite metallocene catalyst.
The polymerization of norbornene：Ethene is substituted by Schlenk bottles twice, add the two of norbornene (1.5mmol) first
Toluene solution (30mL) is slowly added to methylaluminoxane (0.015mmol) afterwards in reactor, stirs 1 hour at room temperature
Add metallocene compound (press reaction solution stereometer 0.05%) afterwards, be rapidly heated to 50 DEG C, holding ethylene pressure in 3atm, after
Stop stirring after 4 hours of continuous reaction.Reaction solution is added among ethanol afterwards, has the generation of white gum thing, is washed with ethanol
Wash to obtain norbornene polymer.It is 330805, Mn/Mw 1.25 to measure polymer Mn through GPC.
Claims (3)
1. a kind of composite metallocene catalyst for norbornene polymerization, it is characterized in that：Using metallocene compound as core into
Point, by metallocene compound and lithium chloride according to 1-2:The molar ratio compounding of 2-1；
The concrete structure of the 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, as follows
Carry out：
(1) react：Take (indenyl) TiI3It is dissolved in THF solution, will be accurate in advance under conditions of -35 DEG C and nitrogen protection
The LiO- (6- substitution -1- anthryls) got ready is added dropwise to containing (indenyl) TiI3THF solution in so that (6- takes LiO-
Generation -1- anthryls)：(indenyl)TiI3Molar ratio be 1.1-1.3：1, mixed liquor slowly recovers anti-to being stirred while room temperature
Answer 14-16h；
(2) it is quenched：Under ice-water bath, 1.5-2.5 times based on mixeding liquid volume obtained by step (1) of saturated ammonium chloride solution is taken,
Slowly instill in mixed liquor obtained by step (1), reaction is quenched；
(3) extract：, will with the ethyl acetate of 3 times of volumes of reaction solution obtained by step (2) extraction step (2) resulting solution in three times
Gained organic phase merges, and is dried with anhydrous magnesium sulfate, solvent is evaporated off in 50 DEG C of backspins, obtains crude product；
(4) recrystallize：Crude product is dissolved by the ethanol of 1 times of crude product stereometer obtained by step (3), adds crude product body afterwards
Product counts 4 times of petroleum ether, is recrystallized in -30 DEG C of refrigerator-freezer, that is, obtains metallocene compound；
(5) compound：According to molar ratio it is 1-2 by metallocene compound made from step (4) and lithium chloride:2-1 ratios mix,
Stirring reaction 1-2h, solvent is then drained under 0.8-1.2MPa, that is, obtains the compound cyclopentadienyl for norbornene polymerization in methanol
Metallic catalyst.
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：Institute
State one kind that the substituent in LiO- (6- substitution -1- anthryls) is ethyl, propyl group or chloromethyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610495924.2A CN106008766B (en) | 2016-06-29 | 2016-06-29 | A kind of composite metallocene catalyst for norbornene polymerization and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610495924.2A CN106008766B (en) | 2016-06-29 | 2016-06-29 | A kind of composite metallocene catalyst for norbornene polymerization and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106008766A CN106008766A (en) | 2016-10-12 |
| CN106008766B true CN106008766B (en) | 2018-04-17 |
Family
ID=57105103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610495924.2A Active CN106008766B (en) | 2016-06-29 | 2016-06-29 | A kind of composite metallocene catalyst for norbornene polymerization and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106008766B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354775B (en) * | 2021-07-13 | 2022-11-15 | 无锡阿科力科技股份有限公司 | Preparation method of cycloolefin copolymer and application of cycloolefin copolymer in preparation of heat-resistant optical material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301272A (en) * | 1998-02-07 | 2001-06-27 | 巴塞尔聚丙烯股份有限公司 | Catalyst system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8445620B2 (en) * | 2011-08-04 | 2013-05-21 | Exxonmobil Research And Engineering Company | Elastic propylene-alpha-olefin copolymer compositions and processes to produce them |
-
2016
- 2016-06-29 CN CN201610495924.2A patent/CN106008766B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301272A (en) * | 1998-02-07 | 2001-06-27 | 巴塞尔聚丙烯股份有限公司 | Catalyst system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106008766A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Scandium-catalyzed regio-and stereoselective cyclopolymerization of functionalized α, ω-dienes and copolymerization with ethylene | |
| CN106661142B (en) | Ligand compound, transistion metal compound and the carbon monoxide-olefin polymeric comprising the compound | |
| CN106062012B (en) | Support type mixed catalyst and the method for preparing the polymer based on alkene using it | |
| CN104254546B (en) | The manufacture method of olefin polymer | |
| JP6029757B2 (en) | Method for producing catalyst for polyolefin polymerization and method for producing polyolefin | |
| CN106488923A (en) | Ligand compound, transistion metal compound and the carbon monoxide-olefin polymeric comprising this compound | |
| JP2016540034A (en) | Metallocene complex, method for producing the same, and catalyst composition | |
| Martins et al. | Highly efficient cis-1, 4 polymerisation of isoprene using simple homoleptic amido rare earth-based catalysts | |
| CN105037588B (en) | A kind of iso-indoles rare-earth metal catalyst, preparation method and application | |
| CN101528784A (en) | Method for producing syndiotactic propylene polymer | |
| CN107531828A (en) | The method for preparing carried metallocene catalyst | |
| CN103502290B (en) | Olefin block copolymers | |
| Yu et al. | Isoprene regioblock copolymerization: switching the regioselectivity by the in situ ancillary ligand transmetalation of active yttrium species | |
| CN106519087A (en) | Liquid polyethylene rubber and preparation method thereof | |
| Chenal et al. | Combining polyethylene CCG and stereoregular isoprene polymerization: first synthesis of Poly (ethylene)-b-(trans-isoprene) by neodymium catalyzed sequenced copolymerization | |
| CN101218262A (en) | Transition metal complexes, catalyst compositions containing the same, and olefin polymerization using the catalyst compositions | |
| CN106008766B (en) | A kind of composite metallocene catalyst for norbornene polymerization and preparation method thereof | |
| CN106632767A (en) | Rare-earth catalyst of nitrogen-containing heterocyclic carbene ligand and olefin polymerization catalyzing method of rare-earth catalyst | |
| CN105646741A (en) | Method for preparing zirconocene type olefin polymerization catalyst | |
| JP2005506418A5 (en) | ||
| CN104558331A (en) | Pincerlike bi-N-heterocyclic carbene biphenyl amine rare earth metal catalyst, preparation method and application thereof | |
| CN107312115A (en) | A kind of pair of indoles rare-earth metal catalyst, preparation method and application | |
| CN107406475A (en) | Transistion metal compound, the carbon monoxide-olefin polymeric comprising it and the method that olefin polymer is prepared using the carbon monoxide-olefin polymeric | |
| CN106632768A (en) | Rare-earth butyl rubber and preparation method thereof | |
| CN103772439B (en) | A kind of quinoline benzimidazole Group IVB list half metallocene and its preparation method and application and the method for olefinic polyreaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |