CN105968238A - Composite catalyst for norbornene polymerization and method of preparing same - Google Patents

Composite catalyst for norbornene polymerization and method of preparing same Download PDF

Info

Publication number
CN105968238A
CN105968238A CN201610496312.5A CN201610496312A CN105968238A CN 105968238 A CN105968238 A CN 105968238A CN 201610496312 A CN201610496312 A CN 201610496312A CN 105968238 A CN105968238 A CN 105968238A
Authority
CN
China
Prior art keywords
reaction
catalyst
adds
solvent
norbornene polymerization
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.)
Granted
Application number
CN201610496312.5A
Other languages
Chinese (zh)
Other versions
CN105968238B (en
Inventor
王大伟
张文泉
余信
丁玉强
朱学军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WUXI ACRYL TECHNOLOGY Co Ltd
Original Assignee
WUXI ACRYL TECHNOLOGY Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by WUXI ACRYL TECHNOLOGY Co Ltd filed Critical WUXI ACRYL TECHNOLOGY Co Ltd
Priority to CN201610496312.5A priority Critical patent/CN105968238B/en
Publication of CN105968238A publication Critical patent/CN105968238A/en
Application granted granted Critical
Publication of CN105968238B publication Critical patent/CN105968238B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a composite catalyst for norbornene polymerization and a method of preparing the same and belongs to the technical field of polymer material preparation. The composite catalyst is made with a metallocene compound and lithium chloride with the metallocene compound as a core ingredient. The composite catalyst prepared herein provides good catalytic activity when applied in norbornene polymerization, an obtained polymer has good properties, and the composite catalyst has a promising application prospect.

Description

A kind of combination catalyst for norbornene polymerization and preparation method thereof
Technical field
The present invention relates to a kind of combination catalyst for norbornene polymerization and preparation method thereof, composition is with cyclopentadienyl Metallic compound is main, belongs to polymeric material preparing technical field.
Background technology
Metallocene catalyst has the catalytic polymerization ability of excellence, and most of monomer almost can be made to occur with ethylene Polymerization.By changing structure and the polymerizing condition of metallocene catalyst, various special construction and property can be obtained The polymer of energy, due to the electronic structure containing cyclopentadienyl ligands and the variation of space structure, by repairing Decorations part, is possible not only to change the activity of catalyst and can synthesize the polymer that microstructure is finer.
Metallocene catalyst belongs to the catalyst with single-activity, and polymerization product has good homogeneity, It is mainly manifested in molecular weight distribution narrower, is evenly distributed in the polymer backbone, be of value to people's property developed Polyolefin products that can be more useful.
Norbornene polymer is the polymer of a kind of unique properties, is applied to microelectronic component, liquid crystal display The aspects such as device protective coating, resistant to elevated temperatures protective material.In recent years, China had started norbornene polymerization Study, the most flourish in the whole nation, except norborene, gathering of some norbornene derivatives Close also in fast development, to meet the industrial demand to this type of material.
The polyolefin products excellent performance that obtains based on metallocene catalyst, the domestic this respect that there is presently no Industrialized production, is simply confined in laboratory research.But, along with industrial to norbornene polymer The requirement of performance is more and more higher, and the polymerization product that different metallocenes obtains has the biggest performance difference, greatly Partial properties is difficult to meet the demand of people, it is therefore desirable 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 apply the combination in norbornene polymerization Catalyst, is made up of metallocene compound and lithium chloride, with metallocene compound as nucleus.Through poly- Close and later stage performance characterization.When for norbornene polymerization, combination catalyst is than simple metallocene catalysis Polymer performance obtained by agent is more excellent, and catalysis activity is higher.
The technical scheme provided according to the present invention, a kind of combination catalyst for norbornene polymerization, with cyclopentadienyl Metallic compound is nucleus, is made up of according to the mol ratio of 1-5:5-1 metallocene compound and lithium chloride；
The concrete structure of described metallocene compound is as follows:
Wherein R=H, Me or Cl.
The preparation method of the described combination catalyst for norbornene polymerization, step by weight is as follows:
(1) preparation of metallocene catalyst:
A, reaction: in the reaction tube of 100mL, add the substituted α-olefins of 0.8-1.2mmol, 18-22mL chlorobenzene, forms suspension；It is added thereto to afterwards at 1.8-2.2mmol tiron, 18-22 DEG C Stirring reaction 20-22h, reaction is drained solvent under 0.5-1.5MPa atmospheric pressure after terminating, is obtained light yellow solid Body；
B, post processing: with the fewest ethanol dissolving step a gained light yellow solid, do not stop to add just own Alkane also stirs until there being solid to separate out in solution；Put into cooling 1-3h in refrigerator, after having a large amount of solid to separate out, Siphon away the supernatant, obtain lower floor's solid；Gained solid is dried at 55-65 DEG C, obtains metallocene catalysis Agent；
(2) compounding: metallocene catalyst step (1) prepared and lithium chloride are 1-5:5-1 according to mol ratio Ratio mixing, in methanol stir 0.5-1.5h, reaction terminate after, drain under 0.8-1.2MPa atmospheric pressure Solvent, obtains the product combination catalyst for norbornene polymerization.
The described substituted α-olefins of step (1) is specially 5-(2-chloroethyl)-α-olefins.
Step (1) described tiron is TiO-(6-F-5-Me-C12H5)、TiO-(6-F-5-Et-C12H5) or TiO-(6-F-5-ClEt-C12H5One in).
Beneficial effects of the present invention: the combination catalyst for norbornene polymerization prepared by the present invention, is used for Having good catalysis activity in norbornene polymerization, the polymer obtained has preferable performance, has one Fixed application prospect.
Detailed description of the invention
Hereinafter, the present invention has been done specific experiment by applicant, and describe a class combination catalyst in detail should It is used in the experimentation in the middle of norbornene polymerization.These are only used for elaborating the present invention, not with any Mode limits the scope of invention.
Embodiment 1
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then at-78 DEG C wherein Dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue to stir Mix 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, rises To stirred overnight at room temperature；Reaction terminates, and removes solvent with Rotary Evaporators, adds normal hexane and the dichloro of 3:1 Methane solvent recrystallization twice, obtains sterling.
(2) preparation of metallocene catalyst: add 5-(2-chloroethyl)-two indenyls in the reaction tube of 100mL Zirconium dichloride (1mmol, 1.0eq.), 20mL chlorobenzene, form suspension；It is added thereto to afterwards TiO-(6-F-5-Me-C12H5) (2.0eq.), stir 21h at 20 DEG C, reaction is drained solvent after terminating, is obtained shallow Yellow solid, with ethanol, normal hexane recrystallization, gained solid is dried, is obtained metallocene catalyst, productivity 46%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:1 with lithium chloride, in first Stirring 1 hour in alcohol, reaction is drained solvent after terminating and is i.e. obtained the combination catalyst for norbornene polymerization.
The polymerization of norborene: Schlenk bottle is substituted ethylene three times, adds the norborene chlorine prepared in advance Benzole soln (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Enter combination catalyst (0.1%), be warming up to 50 DEG C, keep constant ethylene pressure, reaction stirring one hour Rear stopping, joining reactant liquor in the middle of ethanol, has white gum thing to generate, by washing with alcohol three times, Norbornene polymer.Recording polymer Mn through GPC is 367256, and Mn/Mw is 1.31.
Embodiment 2
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then at-78 DEG C wherein Dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue Stirring 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, It is warmed to room temperature and is stirred overnight；Reaction terminates, and removes solvent with Rotary Evaporators, adds the normal hexane and two of 3:1 Chloromethanes solvent recrystallization twice, obtains sterling.
(2) preparation of metallocene catalyst: add 5-(2-chloroethyl)-two indenyls in the reaction tube of 100mL Zirconium dichloride (1mmol, 1.0eq.), 20mL chlorobenzene, form suspension；It is added thereto to afterwards TiO-(6-F-5-Me-C12H5) (2.0eq.), stir 21h at 20 DEG C, reaction is drained solvent after terminating, is obtained shallow Yellow solid, with ethanol, normal hexane recrystallization, gained solid is dried, is obtained metallocene catalyst, productivity 46%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:2 with lithium chloride, in first Stirring 1 hour in alcohol, reaction is drained solvent after terminating and is i.e. obtained the combination catalyst for norbornene polymerization.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 50 DEG C, keeps constant ethylene pressure, reaction stirring to stop after one hour Only, reactant liquor is joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall ice Sheet alkene polymer.
Recording polymer Mn through GPC is 365466, and Mn/Mw is 1.28.
Embodiment 3
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then at-78 DEG C wherein Dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue Stirring 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, It is warmed to room temperature and is stirred overnight；Reaction terminates, and removes solvent with Rotary Evaporators, add 3:1 normal hexane and Twice of dichloromethane solvent recrystallization, obtains sterling.
(2) preparation of metallocene catalyst: add 5-(2-chloroethyl)-two indenyls in the reaction tube of 100mL Zirconium dichloride (1mmol, 1.0eq.), 20mL chlorobenzene, form suspension；It is added thereto to afterwards TiO-(6-F-5-Me-C12H5) (2.0eq.), stir 21h at 20 DEG C, reaction is drained solvent after terminating, is obtained Light yellow solid, with ethanol, normal hexane recrystallization, gained solid is dried, is obtained metallocene catalyst, produces Rate 46%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:3 with lithium chloride, in first Stirring 1 hour in alcohol, reaction is drained solvent after terminating and is i.e. obtained the combination catalyst for norbornene polymerization.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 50 DEG C, keeps constant ethylene pressure, after reaction is stirred one hour Stop, reactant liquor being joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall Norbomene polymer.
Recording polymer Mn through GPC is 366742, and Mn/Mw is 1.25.
Embodiment 4
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then at-78 DEG C wherein Dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue to stir Mix 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, rises To stirred overnight at room temperature；Reaction terminates, and removes solvent with Rotary Evaporators, adds the normal hexane and two of 3:1 Chloromethanes solvent recrystallization twice, obtains sterling.
(2) preparation of metallocene catalyst: add 5-(2-chloroethyl)-two indenyls in the reaction tube of 100mL Zirconium dichloride (1mmol, 1.0eq.), 20mL chlorobenzene, form suspension；It is added thereto to afterwards TiO-(6-F-5-Me-C12H5) (2.0eq.), stir 21h at 20 DEG C, reaction is drained solvent after terminating, is obtained shallow Yellow solid, with ethanol, normal hexane recrystallization, gained solid is dried, is obtained metallocene catalyst, productivity 46%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:4 with lithium chloride, in first Stirring 1 hour in alcohol, reaction is drained solvent after terminating and is i.e. obtained the combination catalyst for norbornene polymerization.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 50 DEG C, keeps constant ethylene pressure, reaction stirring to stop after one hour Only, reactant liquor is joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall ice Sheet alkene polymer.
Recording polymer Mn through GPC is 345635, and Mn/Mw is 1.34.
Embodiment 5
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then at-78 DEG C wherein Dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue to stir Mix 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, rises To stirred overnight at room temperature；Reaction terminates, and removes solvent with Rotary Evaporators, adds the normal hexane and two of 3:1 Chloromethanes solvent recrystallization twice, obtains sterling.
(2) preparation of metallocene catalyst: add 5-(2-chloroethyl)-two indenyls in the reaction tube of 100mL Zirconium dichloride (1mmol, 1.0eq.), 20mL chlorobenzene, form suspension；It is added thereto to afterwards TiO-(6-F-5-Me-C12H5) (2.0eq.), stir 21h at 20 DEG C, reaction is drained solvent after terminating, is obtained shallow Yellow solid, with ethanol, normal hexane recrystallization, gained solid is dried, is obtained metallocene catalyst, productivity 46%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:5 with lithium chloride, at methanol Middle stirring 1 hour, reaction is drained solvent after terminating and is i.e. obtained the combination catalyst for norbornene polymerization.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 50 DEG C, keeps constant ethylene pressure, reaction stirring to stop after one hour Only, reactant liquor is joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall ice Sheet alkene polymer.
Recording polymer Mn through GPC is 387953, and Mn/Mw is 1.27.
Embodiment 6
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then at-78 DEG C wherein Dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue to stir Mix 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, rises To stirred overnight at room temperature；Reaction terminates, and removes solvent with Rotary Evaporators, adds the normal hexane and two of 3:1 Chloromethanes solvent recrystallization twice, obtains sterling.
(2) preparation of metallocene catalyst: 5-(2-chloroethyl)-α-olefins will be taken and put into reaction tube In, add chlorobenzene solvent and form suspension, be subsequently adding TiO-(6-F-5-Et-C12H5), stir 21h at 20 DEG C, Drain solvent, obtain light yellow solid, use normal hexane recrystallization, dry, obtain metallocene catalyst, productivity 54%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:1 with lithium chloride, in first Stirring 1 hour in alcohol, reaction is drained solvent after terminating and is i.e. obtained the combination catalyst for norbornene polymerization.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 60 DEG C, keeps constant ethylene pressure, reaction stirring to stop after one hour Only, reactant liquor is joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall ice Sheet alkene polymer.
Recording polymer Mn through GPC is 374453, and Mn/Mw is 1.20.
Embodiment 7
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then at-78 DEG C wherein Dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue Stirring 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, It is warmed to room temperature and is stirred overnight；Reaction terminates, and removes solvent with Rotary Evaporators, add 3:1 normal hexane and Twice of dichloromethane solvent recrystallization, obtains sterling.
(2) preparation of metallocene catalyst: 5-(2-chloroethyl)-α-olefins will be taken and put into reaction tube In, add chlorobenzene solvent and form suspension, be subsequently adding TiO-(6-F-5-Et-C12H5), stir 21h at 20 DEG C, Drain solvent, obtain light yellow solid, use normal hexane recrystallization, dry, obtain metallocene catalyst, productivity 54%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:2 with lithium chloride, at methanol Middle stirring 1 hour, reaction is drained solvent after terminating and is i.e. obtained the combination catalyst for norbornene polymerization.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 60 DEG C, keeps constant ethylene pressure, reaction stirring to stop after one hour Only, reactant liquor is joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall ice Sheet alkene polymer.
Recording polymer Mn through GPC is 378694, and Mn/Mw is 1.26.
Embodiment 8
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then at-78 DEG C wherein Dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue to stir Mix 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, rises To stirred overnight at room temperature；Reaction terminates, and removes solvent with Rotary Evaporators, adds the normal hexane and two of 3:1 Chloromethanes solvent recrystallization twice, obtains sterling.
(2) preparation of metallocene catalyst: 5-(2-chloroethyl)-α-olefins will be taken and put into reaction tube In, add chlorobenzene solvent and form suspension, be subsequently adding TiO-(6-F-5-Et-C12H5), stir 21h at 20 DEG C, Drain solvent, obtain light yellow solid, use normal hexane recrystallization, dry, obtain metallocene catalyst, productivity 54%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:3 with lithium chloride, at methanol Middle stirring 1 hour, reaction is drained solvent after terminating and is i.e. obtained the combination catalyst for norbornene polymerization.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 60 DEG C, keeps constant ethylene pressure, reaction stirring to stop after one hour Only, reactant liquor is joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall ice Sheet alkene polymer.
Recording polymer Mn through GPC is 324586, and Mn/Mw is 1.27.
Embodiment 9
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then at-78 DEG C wherein Dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue Stirring 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, It is warmed to room temperature and is stirred overnight；Reaction terminates, and removes solvent with Rotary Evaporators, add 3:1 normal hexane and Twice of dichloromethane solvent recrystallization, obtains sterling.
(2) preparation of metallocene catalyst: 5-(2-chloroethyl)-α-olefins will be taken and put into reaction tube In, add chlorobenzene solvent and form suspension, be subsequently adding TiO-(6-F-5-Et-C12H5), stir 21h at 20 DEG C, Drain solvent, obtain light yellow solid, use normal hexane recrystallization, dry, obtain metallocene catalyst, productivity 54%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:4 with lithium chloride, at methanol Middle stirring 1 hour, reaction is drained solvent after terminating and is i.e. obtained the combination catalyst for norbornene polymerization.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 60 DEG C, keeps constant ethylene pressure, reaction stirring to stop after one hour Only, reactant liquor is joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall ice Sheet alkene polymer.
Recording polymer Mn through GPC is 314357, and Mn/Mw is 1.25.
Embodiment 10
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then to it at-78 DEG C In dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature continue Stirring 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, It is warmed to room temperature and is stirred overnight；Reaction terminates, and removes solvent with Rotary Evaporators, add 3:1 normal hexane and Twice of dichloromethane solvent recrystallization, obtains sterling.
(2) preparation of metallocene catalyst: 5-(2-chloroethyl)-α-olefins will be taken and put into reaction tube In, add chlorobenzene solvent and form suspension, be subsequently adding TiO-(6-F-5-Et-C12H5), stir 21h at 20 DEG C, Drain solvent, obtain light yellow solid, use normal hexane recrystallization, dry, obtain metallocene catalyst, productivity 54%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:5 with lithium chloride, at methanol Middle stirring 1 hour, reaction is drained solvent after terminating and is i.e. obtained the combination catalyst for norbornene polymerization.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 60 DEG C, keeps constant ethylene pressure, reaction stirring to stop after one hour Only, reactant liquor is joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall ice Sheet alkene polymer.Recording polymer Mn through GPC is 354672, and Mn/Mw is 1.28.
Embodiment 11
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then to it at-78 DEG C In dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue Continuous stirring 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, It is warmed to room temperature and is stirred overnight；Reaction terminates, and removes solvent with Rotary Evaporators, add 3:1 normal hexane and Twice of dichloromethane solvent recrystallization, obtains sterling.
(2) preparation of metallocene catalyst: 5-(2-chloroethyl)-α-olefins will be taken and put into reaction tube In, add chlorobenzene solvent and form suspension, be subsequently adding TiO-(6-F-5-(2-ClEt)-C12H5), stir at 20 DEG C Mix 21h, drain solvent, obtain light yellow solid, use normal hexane recrystallization, dry, obtain metallocene catalyst, Productivity 67%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:1 with lithium chloride, in first Alcohol stirs 1 hour, after reaction terminates, drains solvent and i.e. obtain being catalyzed for the combination of norbornene polymerization Agent.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 70 DEG C, keeps constant ethylene pressure, reaction stirring to stop after one hour Only, reactant liquor is joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall ice Sheet alkene polymer.Recording polymer Mn through GPC is 312506, and Mn/Mw is 1.28.
Embodiment 12
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then to it at-78 DEG C In dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue Continuous stirring 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, It is warmed to room temperature and is stirred overnight；Reaction terminates, and removes solvent with Rotary Evaporators, add 3:1 normal hexane and Twice of dichloromethane solvent recrystallization, obtains sterling.
(2) preparation of metallocene catalyst: 5-(2-chloroethyl)-α-olefins will be taken and put into reaction tube In, add chlorobenzene solvent and form suspension, be subsequently adding TiO-(6-F-5-(2-ClEt)-C12H5), stir at 20 DEG C Mix 21h, drain solvent, obtain light yellow solid, use normal hexane recrystallization, dry, obtain metallocene catalyst, Productivity 67%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:2 with lithium chloride, at methanol Middle stirring 1 hour, after reaction terminates, drains solvent and i.e. obtains the combination catalyst for norbornene polymerization.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 70 DEG C, keeps constant ethylene pressure, reaction stirring to stop after one hour Only, reactant liquor is joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall ice Sheet alkene polymer.
Recording polymer Mn through GPC is 354690, and Mn/Mw is 1.38.
Embodiment 13
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then at-78 DEG C wherein Dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue to stir Mix 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, rises To stirred overnight at room temperature；Reaction terminates, and removes solvent with Rotary Evaporators, adds the normal hexane and two of 3:1 Chloromethanes solvent recrystallization twice, obtains sterling.
(2) preparation of metallocene catalyst: 5-(2-chloroethyl)-α-olefins will be taken and put into reaction tube In, add chlorobenzene solvent and form suspension, be subsequently adding TiO-(6-F-5-(2-ClEt)-C12H5), stir at 20 DEG C Mix 21h, drain solvent, obtain light yellow solid, use normal hexane recrystallization, dry, obtain metallocene catalyst, Productivity 67%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:3 with lithium chloride, at methanol Middle stirring 1 hour, after reaction terminates, drains solvent and i.e. obtains the combination catalyst for norbornene polymerization.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 70 DEG C, keeps constant ethylene pressure, after reaction is stirred one hour Stop, reactant liquor being joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall Norbomene polymer.
Recording polymer Mn through GPC is 309836, and Mn/Mw is 1.29.
Embodiment 14
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then at-78 DEG C wherein Dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue to stir Mix 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, rises To stirred overnight at room temperature；Reaction terminates, and removes solvent with Rotary Evaporators, adds the normal hexane and two of 3:1 Chloromethanes solvent recrystallization twice, obtains sterling.
(2) preparation of metallocene catalyst: 5-(2-chloroethyl)-α-olefins will be taken and put into reaction tube In, add chlorobenzene solvent and form suspension, be subsequently adding TiO-(6-F-5-(2-ClEt)-C12H5), stir at 20 DEG C Mix 21h, drain solvent, obtain light yellow solid, use normal hexane recrystallization, dry, obtain metallocene catalyst, Productivity 67%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:4 with lithium chloride, in first Alcohol stirs 1 hour, after reaction terminates, drains solvent and i.e. obtain being catalyzed for the combination of norbornene polymerization Agent.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 70 DEG C, keeps constant ethylene pressure, reaction stirring to stop after one hour Only, reactant liquor is joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall ice Sheet alkene polymer.
Recording polymer Mn through GPC is 343267, and Mn/Mw is 1.32.
Embodiment 15
(1) preparation of 5-(2-chloroethyl)-α-olefins: under nitrogen atmosphere, to the round bottom of 100mL Flask adds 5-(2-chloroethyl) indenes (2mmol, 2.0eq.), 50mL ether；Then to it at-78 DEG C In dropwise drip butyl lithium (2.5M/L, 2.1mmol, 2.1eq.), after dropping, be slowly increased to room temperature and continue Continuous stirring 1h；Again it is cooled to-78 DEG C, drips ZrCl wherein4(1mmol, 1.0eq.), after dropping, It is warmed to room temperature and is stirred overnight；Reaction terminates, and removes solvent with Rotary Evaporators, add 3:1 normal hexane and Twice of dichloromethane solvent recrystallization, obtains sterling.
(2) preparation of metallocene catalyst: 5-(2-chloroethyl)-α-olefins will be taken and put into reaction tube In, add chlorobenzene solvent and form suspension, be subsequently adding TiO-(6-F-5-(2-ClEt)-C12H5), stir at 20 DEG C Mix 21h, drain solvent, obtain light yellow solid, use normal hexane recrystallization, dry, obtain metallocene catalyst, Productivity 67%.
(3) compounding: the metallocene catalyst obtained to be mixed according to mol ratio 1:5 with lithium chloride, at methanol Middle stirring 1 hour, after reaction terminates, drains solvent and i.e. obtains the combination catalyst for norbornene polymerization.
Norbornene polymerization: Schlenk bottle is substituted ethylene three times, adds the norborene chlorobenzene prepared in advance Solution (1.5mmol), in reactor, adds MAO (0.15mmol) stirring half an hour, adds Combination catalyst (0.1%), is warming up to 70 DEG C, keeps constant ethylene pressure, reaction stirring to stop after one hour Only, reactant liquor is joined in the middle of ethanol, have white gum thing to generate, by washing with alcohol three times, obtain fall ice Sheet alkene polymer.
Recording polymer Mn through GPC is 387967, and Mn/Mw is 1.34.

Claims (4)

1., for a combination catalyst for norbornene polymerization, it is characterized in that: with metallocene compound as core Heart composition, is made up of according to the mol ratio of 1-5:5-1 metallocene compound and lithium chloride；
The concrete structure of described metallocene compound is as follows:
Wherein R=H, Me or Cl.
2. it is used for the preparation method of the combination catalyst of norbornene polymerization described in claim 1, it is characterized in that Step by weight is as follows:
(1) preparation of metallocene catalyst:
A, reaction: in the reaction tube of 100mL, add the substituted α-olefins of 0.8-1.2mmol, 18-22mL chlorobenzene, forms suspension；It is added thereto to afterwards at 1.8-2.2mmol tiron, 18-22 DEG C Stirring reaction 20-22h, reaction is drained solvent under 0.5-1.5MPa atmospheric pressure after terminating, is obtained light yellow solid Body；
B, post processing: with the fewest ethanol dissolving step a gained light yellow solid, do not stop to add just own Alkane also stirs until there being solid to separate out in solution；Put into cooling 1-3h in refrigerator, after having a large amount of solid to separate out, Siphon away the supernatant, obtain lower floor's solid；Gained solid is dried at 55-65 DEG C, obtains metallocene catalysis Agent；
(2) compounding: metallocene catalyst step (1) prepared and lithium chloride are 1-5:5-1 according to mol ratio Ratio mixing, in methanol stir 0.5-1.5h, reaction terminate after, drain under 0.8-1.2MPa atmospheric pressure Solvent, obtains the product combination catalyst for norbornene polymerization.
3. it is used for the preparation method of the combination catalyst of norbornene polymerization, its feature as claimed in claim 2 It is: the described substituted α-olefins of step (1) is specially 5-(2-chloroethyl)-α-olefins.
4. it is used for the preparation method of the combination catalyst of norbornene polymerization, its feature as claimed in claim 2 It is: step (1) described tiron is TiO-(6-F-5-Me-C12H5)、TiO-(6-F-5-Et-C12H5) or TiO-(6-F-5-ClEt-C12H5One in).
CN201610496312.5A 2016-06-29 2016-06-29 A kind of combination catalyst for norbornene polymerization and preparation method thereof Active CN105968238B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610496312.5A CN105968238B (en) 2016-06-29 2016-06-29 A kind of combination catalyst for norbornene polymerization and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610496312.5A CN105968238B (en) 2016-06-29 2016-06-29 A kind of combination catalyst for norbornene polymerization and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105968238A true CN105968238A (en) 2016-09-28
CN105968238B CN105968238B (en) 2018-04-06

Family

ID=57020322

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610496312.5A Active CN105968238B (en) 2016-06-29 2016-06-29 A kind of combination catalyst for norbornene polymerization and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105968238B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113321767A (en) * 2021-07-13 2021-08-31 无锡阿科力科技股份有限公司 Preparation method and application of cycloolefin copolymer
CN113354776A (en) * 2021-07-13 2021-09-07 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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113321767A (en) * 2021-07-13 2021-08-31 无锡阿科力科技股份有限公司 Preparation method and application of cycloolefin copolymer
CN113354776A (en) * 2021-07-13 2021-09-07 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

Also Published As

Publication number Publication date
CN105968238B (en) 2018-04-06

Similar Documents

Publication Publication Date Title
CN106062012B (en) Support type mixed catalyst and the method for preparing the polymer based on alkene using it
CN106661142B (en) Ligand compound, transistion metal compound and the carbon monoxide-olefin polymeric comprising the compound
CN100358923C (en) Polymerization process using a metallocene catalyst system
CN102336846B (en) Loaded alpha-palladium diimine and method for preparing hyperbranched polyethylene by catalyzing with same
CN102481556B (en) Cyclic organosilicon compounds as electron donors for polyolefin catalysts
CN104854143B (en) Polymerization
JP6450393B2 (en) Metallocene compound, catalyst composition containing the same, and method for producing polyolefin using the same
KR101492571B1 (en) Hybride supported metallocene catalysts and method for preparing the same
CN104334590B (en) For preparing the immobilization on an inorganic of the single-site catalysts of UHMWPE
CN105518034B (en) Polyolefin
CN108401432A (en) For synthesizing the carbon monoxide-olefin polymeric of olefin copolymer and preparing the method for olefin copolymer
JP6499280B2 (en) Metallocene-supported catalyst and method for producing polyolefin using the same
CN107075008A (en) The method of Metallocenic compound, the catalyst of carried metal cyclopentadienyl and the catalyst preparation polyolefin using carried metal cyclopentadienyl
CN105482004B (en) A kind of composite catalyst for being used to prepare wide/dual-peak distributed high density polyethylene
CN105646741B (en) A kind of preparation method of luxuriant zirconium type olefin polymerization catalysis
JP6511061B2 (en) Metallocene compound, catalyst composition containing the same, and method of producing olefin polymer using the same
CN105968238A (en) Composite catalyst for norbornene polymerization and method of preparing same
CN106519087A (en) Liquid polyethylene rubber and preparation method thereof
CN108264591B (en) Main catalyst of olefin polymerization catalyst, preparation method of main catalyst and olefin polymerization catalyst
CN108884184A (en) Miscellaneous loads type catalyst
CN101607934B (en) 2-ammonia methyl-pyridine nickel complex, preparation method and application thereof
CN107312115A (en) A kind of pair of indoles rare-earth metal catalyst, preparation method and application
CN105273000B (en) Asymmetry limitation configuration dinuclear metallocene compounds and preparation method and application
CN101220060A (en) Single-indenyl rareearth complexes, synthesizing method and application thereof
CN104892801A (en) Organic porous material after-supported single cyclopentadienyl chromium catalyst and application thereof

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