CN109627366A - A kind of metallocene catalyst and the application in cyclic olefine copolymer preparation - Google Patents
A kind of metallocene catalyst and the application in cyclic olefine copolymer preparation Download PDFInfo
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Abstract
The invention discloses a kind of metallocene catalyst and the applications in cyclic olefine copolymer preparation, belong to technical field of material chemistry.Isoparaffin, cycloolefin and ethylene are separately added into reactor, ethylene-cycloolefin hydrocarbon copolymer is prepared using metallocene catalyst provided by the invention.The present invention is while guaranteeing the high catalytic activity and good stability of catalyst, applicable polymer solvent is cheap relative to benzene kind solvent, it is environmentally friendly, it is suitble to duration production, the ethylene-cycloolefin hydrocarbon copolymer of production preparation has molecular weight low, the characteristics of narrowly distributing, gained copolymer have good processability.
Description
Technical field
A kind of metallocene catalyst and the application in cyclic olefine copolymer preparation, belong to technical field of material chemistry.
Background technique
Cyclic olefine copolymer, abbreviation COC (Cyclic-Olefin Copolymers) is one kind by cycloolefin addition copolymerization
High added value thermoplastic engineering plastic made of conjunction, because it is with high transparency, high glass-transition temperature and high resistance to chemicals product
The features such as property and receive much attention.It has been widely used in the various optical lens of manufacture, auto bulb, LCD component, electronics at present
And electric component, medicine and packaging material for food etc..
Early stage cycloolefin copolymer is closed using Ziegler-Natta catalyst, and polymerization activity is very low, as metallocene is urged
The appearance of agent, polymerization activity greatly improve.Current Situation of Metallocene Cycloolefine Copolymer (abbreviation mCOC), be develop recently one kind it is novel
Amorphous polyolefins resin.Since metallocene catalyst is single site catalysts (scc), can be generated in copolymerization
The cyclic olefine copolymer that relative molecular weight distribution is narrow, composition is evenly distributed.Therefore mCOC polymer has the advantages of many aspects,
It is glass transition temperature height, production easy to process first；It is followed by various to have preeminent performance, such as light resistance, barrier properties for gases,
The advantages that chemical resistance, optical property, molding processibility.These many advantages all provide for packaging applications very beautiful
Good prospect.
Kaminsky first discovery metallocene/methylaluminoxane (MAO) catalyst system, for being catalyzed the addition of cycloolefin
Polymerization, so that the research in the field be made to obtain remarkable progress.The polymerization of Current Situation of Metallocene Cycloolefine Copolymer mainly has metallocene
It is catalyzed cycloolefin and ethylene copolymer, metallocene catalysis cycloolefin homopolymerization etc..
A kind of cycloolefin preparing composition narrowly distributing using metallocene catalyst involved in Chinese patent CN101125901 is total
The method of polymers；A kind of preparation method of cyclic olefine copolymer of CN200710071285.8, in the presence of a catalyst, by extremely
The polymerization reaction of a kind of few cycloolefin and at least one acyclic olefin and realize, catalyst include at least one co-catalyst and
At least one metallocene.The semicontinuous addition of non-ring olefin monomer, pulse or semicontinuous adds cycloolefin monomers；Or cycloolefin monomers
It is added at one time, non-ring olefin monomer interruption is added portionwise；Or continuous charging mode, obtain cyclic olefine copolymer.
CN201510756024.4 is related to a kind of double activity center's composite catalyst and total using its cycloolefin obtained
Polymers adds inert organic solvents, cycloolefin and ethylene under the conditions of temperature is 40-95 DEG C, pressure is 0.1-5.0MPa respectively
Enter reactor, chain-transferring agent is then added, is eventually adding double activity center's composite catalyst and carries out solution polymerization, reaction knot
It will be filtered after obtained reaction liquid precipitate after beam, and the filter cake being obtained by filtration washed, it is dry.The method of the present invention can be
While guaranteeing the catalytic activity height and stable in catalytic performance of catalyst, the copolymer of preparation is relative to metallocene ethylene-cycloolefin
Hydrocarbon copolymer intensity and modulus with higher, and there is lower molecular weight relative to non-luxuriant ethylene-cycloolefin hydrocarbon copolymer
With preferable processability.
Patent of invention CN201210140493.X is using cycloolefin monomers and alpha-olefin as polymerized monomer, existing for catalyst
Under the conditions of, polymerization reaction is carried out in atent solvent, obtains cyclic olefine copolymer.
In the present invention, cycloolefin monomers are large volume cycloolefin, since steric hindrance acts on, in the feelings of low insertion rate
Under condition, the cyclic olefine copolymer of high glass transition temperature is obtained, flexible alpha-olefin unit increases in the copolymer, to make
Obtaining cyclic olefine copolymer chain rigidity reduces, the entanglement enhancing between chain, to improve the tear resistance of cyclic olefine copolymer
Can, so that its brittleness is improved.The cyclic olefine copolymer of composition narrowly distributing can be prepared using the method for the present invention, it is obtained
The chemical uniformity of cyclic olefine copolymer is high, and heat resistance and light transmission rate are high.
Summary of the invention
The present invention provides a kind of metallocene catalyst and a kind of utilization catalyst preparation isoparaffin-cycloolefin copolymer
The method of object, thus obtained ethylene-cycloolefin hydrocarbon copolymer, this method polymerization activity is high, copolymer obtained have compared with
Low molecular weight, and raw material is easy to get, cost is lower, environmental pollution is smaller, easy to industrialized production.
The present invention provides a kind of metallocene catalyst, has chemical structure shown in formula 1 or formula 2:
In formula 1, R1 C1-C8Selected from linear or branched alkyl group, C13-C21Two arylalkyl groups, C1-C8Alkyl silyl, two virtues
In perfume base silicon substrate, preferably C1-C4Linear or branched alkyl group, C13-C17Two arylalkyl groups, C1-C4Alkyl silyl, C12-C16Two virtues
Perfume base silicon substrate, more preferable methyl, ethyl, isopropyl, diphenyl methyl, dimethyl silicon substrate, diphenyl silicon substrate；Cyclopentadiene-R2
Unsubstituted or substituted cyclopentadienyl group, fluorenyl or indenyl are each independently selected from cyclopentadiene-R3.
In formula 2, cyclopentadiene-R4 and cyclopentadiene-R5 are each independently selected from cyclopentadienyl group, fluorenyl or indenyl, R6
Hydrogen, C are each independently selected from R71-C8Linear or branched alkyl group, preferably hydrogen, C1-C4Linear or branched alkyl group.
The present invention also provides a kind of methods for preparing cyclic olefine copolymer using the metallocene catalyst, by isomeric alkane
Reactor is added in hydrocarbon, cycloolefin and ethylene, and metallocene catalyst is added and a kind of co-catalyst carries out solution polymerization, polymerization
Reaction time is 0.1-10h, and reaction temperature is 40-95 DEG C, reaction pressure 0.1-5.0MPa.
The molar ratio of the cycloolefin and ethylene is 1: 1~50: 1, the molar ratio of the metallocene catalyst and cycloolefin
It is 1: 3000~1: 100000, the molar ratio of the cycloolefin and ethylene is 2: 1~40: 1.The cycloolefin be norbornene,
One or more of vinyl norbornene and ethylidene norbornene.
The co-catalyst be methylaluminoxane (MAO), modification methylaluminoxane (MMAO), ethylaluminoxane (EAO),
Isobutyl aluminium alkoxide (i-BAO), B (C6F5)3Or C (C6H5)3B(C6F5)3One or more of Deng；The co-catalyst and cyclopentadienyl
The molar ratio of metallic catalyst is 50: 1~5000: 1.
The isoparaffin be IsoparC, IsoparE, IsoparG, IsoparH, IsoparJ, IsoparK,
One of IsoparL, IsoparM, IsoparN, IsoparP, IsoparV.
In the present invention, metallocene compound specifically can-(1- indenyl) dichloride bis- selected from dimetylsilyl-
Zirconium, isopropylidene (3- methyl cyclopentadienyl) (1- indenyl) zirconium dichloride, dimetylsilyl (cyclopentadienyl group) (1- indenes
Base) zirconium dichloride, diphenyl methene (cyclopentadienyl group) (9- fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl group) (4,5-
Phendioxin-indenyl) zirconium dichloride, dimetylsilyl (cyclopentadienyl group) (4,5- phendioxins-indenyl) zirconium dichloride.
In method provided by the invention, a kind of chain-transferring agent, the chain-transferring agent and the cyclopentadienyl gold is added in the property of can choose
The molar ratio of metal catalyst is 5-500: 1.Wherein the chain-transferring agent is selected from trimethyl aluminium (Al (CH3)3), triethyl aluminum (Al
(CH2CH3)3), tri-n-n-propyl aluminum (Al (C3H7)3), triisobutyl aluminium (Al (i-C4H9)3), three n-butylaluminums (Al (C4H9)3), three
Isopentyl aluminium (Al (i-C5H11)3), three n-pentyl aluminium (Al (C5H11)3), tri-n-hexyl aluminum (Al (C6H13)3), three isohesyl aluminium
(Al(i-C6H13)3), diethylmethyl aluminium (Al (CH3)(CH3CH2)2), dimethyl ethyl aluminium (Al (CH3CH2)(CH3)2), a chlorine
Dimethyl aluminium (Al (CH3)2Cl), dichloro monomethyl aluminium (Al (CH3)Cl2), aluminium diethyl monochloride (Al (C2H5)2Cl), dichloro one
Aluminium ethide (Al (C2H5)Cl2), a chlorine diη-propyl aluminium (Al (C3H7)2Cl), one n-propyl aluminium (Al (C of dichloro3H7)Cl2), a chlorine
Diisobutyl aluminum (Al (i-C4H9)2Cl), one aluminium isobutyl of dichloro (Al (i-C4H9)Cl2), a chlorine di-n-butyl aluminium (Al (C4H9)2Cl), one n-butylaluminum of dichloro (Al (C4H9)Cl2), a chlorine diisoamyl aluminium (Al (i-C5H11)2Cl), one isopentyl aluminium of dichloro
(Al(i-C5H11)Cl2), a chlorine di-n-hexyl aluminium (Al (C6H13)2Cl), one n-hexyl aluminium (Al (C of dichloro6H13)Cl2), a chlorine two
Isohesyl aluminium (Al (i-C6H13)2Cl), one isohesyl aluminium (Al (i-C of dichloro6H13)Cl2) or their any combination, more preferable three
Aluminium methyl, triethyl aluminum, tri-n-n-propyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, one aluminium ethide of dichloro or their any group
It closes, further preferred trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or their any combination.
Benefit of the present invention:
(1) in the present invention, cycloolefin monomers are large volume cycloolefin, since steric hindrance acts on, in low insertion rate
In the case where, the cyclic olefine copolymer of high glass transition temperature is obtained, flexible alpha-olefin unit increases in the copolymer, from
And make the reduction of cyclic olefine copolymer chain rigidity, the entanglement enhancing between chain, to improve the anti-tear of cyclic olefine copolymer
Fragility energy, so that its brittleness is improved；
(2) method provided according to the present invention, can be in the same of the high catalytic activity and good stability for guaranteeing catalyst
When, applicable polymer solvent is cheap relative to benzene kind solvent, and it is environmentally friendly, it is suitble to duration production, produces preparation
The characteristics of ethylene-cycloolefin hydrocarbon copolymer has molecular weight low, narrowly distributing.The second that the preparation method provided according to the present invention obtains
Alkene-cyclic olefine copolymer also has good processability.
Specific embodiment
The present invention is further illustrated below by example, but the present invention is not limited thereto.
Following embodiment, polymer middle ring olefin(e) centent nmr determination, polymer are molten with deuterated o-dichlorohenzene
Solution does internal standard with hexamethyldisiloxane, and measuring temperature is 120 DEG C.It is poly- using high-temperature gel permeation chromatography instrument (HT-GPC) measurement
Close the number-average molecular weight of object (using trichloro-benzenes as solvent and mobile phase, concentration 1.5g/L, flow velocity 1mL/min), weight average molecular weight with
And molecular weight distributing index.
Embodiment 1:
In 1L tank reactor, 0.65mol purification norbornene is added in the isoparE of 500ml, which is added
Enter into the reactor being purged with nitrogen in advance, Multi-step forming ethylene (1MPa) is saturated solution by ethylene, 100 DEG C,
1MPa and stirring under conditions of, sequentially add 14ml concentration be 1.72mol/L methylaluminoxane (MAO) toluene solution, 20 μ
Mol isopropylidene-(1- indenyl)-cyclopentadienyl zirconium dichloride, polymerization process control pressure by supplementing metered ethylene
For 1MPa.
After reacting 15min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
102 grams of polymer are obtained, catalyst activity 2.04 × 107g/(molM·h).Polymeric properties are shown in Table 1.
Embodiment 2:
In 1L tank reactor, 0.65mol purification norbornene is added in the isoparG of 500ml, which is added
Enter into the reactor being purged with nitrogen in advance, Multi-step forming ethylene (1MPa) is saturated solution by ethylene, 100 DEG C,
1MPa and stirring under conditions of, sequentially add 7ml concentration be 1.72mol/L methylaluminoxane (MAO) toluene solution, 10 μm of ol
Dimetylsilyl-is bis--(1- indenyl) zirconium dichloride, polymerization process is by supplementing metered ethylene, control pressure
1MPa。
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
90 grams of polymer are obtained, catalyst activity 1.8 × 107g/(molM·h).Polymeric properties are shown in Table 1.
Embodiment 3:
In 1L tank reactor, 1.3mol purification vinyl norbornene is added in the IsoparH of 500ml, by this
Solution is added in the reactor being purged with nitrogen in advance, and Multi-step forming ethylene (1MPa) is saturated solution by ethylene,
100 DEG C, 1MPa and stirring under conditions of, sequentially add 7ml concentration be 1.72mol/L methylaluminoxane (MAO) toluene solution,
10 μm of ol dimetylsilyls-bis--(1- indenyl) zirconium dichloride, polymerization process is by supplementing metered ethylene, control pressure
Power is 1MPa.
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
81 grams of polymer are obtained, catalyst activity 1.6 × 107g/(molM·h).Polymeric properties are shown in Table 1.
Embodiment 4:
In 1L tank reactor, 1.3mol purification vinyl norbornene is added in the IsoparJ of 500ml, by this
Solution is added in the reactor being purged with nitrogen in advance, and Multi-step forming ethylene (1MPa) is saturated solution by ethylene, 80
DEG C, 1MPa and stirring under conditions of, sequentially add 7ml concentration be 1.72mol/L methylaluminoxane (MAO) toluene solution, 10 μ
Mol diphenyl methene (cyclopentadienyl group) (9- fluorenyl) zirconium dichloride, polymerization process is by supplementing metered ethylene, control pressure
Power is 1MPa.
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
95 grams of polymer are obtained, catalyst activity 1.9 × 107g/(molM·h).Polymeric properties are shown in Table 1.
Embodiment 5:
In 1L tank reactor, 1.3mol purification vinyl norbornene is added in the IsoparE of 500ml, by this
Solution is added in the reactor being purged with nitrogen in advance, and Multi-step forming ethylene (1MPa) is saturated solution by ethylene, 80
DEG C, 1MPa and stirring under conditions of, sequentially add 16ml concentration be 1.5mol/L modified methylaluminoxane (MMAO) solution, 20 μ
Mol di-n-butyl bis cyclopentadienyl zirconium dichloride, polymerization process are 1MPa by supplementing metered ethylene, control pressure.
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
43 grams of polymer are obtained, catalyst activity 4.3 × 106g/(molM·h).Polymeric properties are shown in Table 1.
Embodiment 6:
In 1L tank reactor, 2.6mol purification ethylidene norbornene is added in the IsoparC of 500ml, this is molten
Liquid is added in the reactor being purged with nitrogen in advance, and Multi-step forming ethylene (1MPa) is saturated solution by ethylene, 80
DEG C, 1MPa and stirring under conditions of, sequentially add 16ml concentration be 1.5mol/L modified methylaluminoxane (MMAO) solution, 20 μ
Mol di-n-butyl bis cyclopentadienyl zirconium dichloride, polymerization process are 1MPa by supplementing metered ethylene, control pressure.
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
36 grams of polymer are obtained, catalyst activity 3.6 × 106g/(molM·h).Polymeric properties are shown in Table 1.
Embodiment 7:
In 1L tank reactor, 1.3mol purification norbornene is added in the isoparE of 500ml, which is added
Enter into the reactor being purged with nitrogen in advance, Multi-step forming ethylene (2MPa) is saturated solution by ethylene, 100 DEG C,
2MPa and stirring under conditions of, sequentially add 14ml concentration be 1.72mol/L methylaluminoxane (MAO) toluene solution, 20 μ
Mol dimetylsilyl (cyclopentadienyl group) (4,5- phendioxins-indenyl) zirconium dichloride, polymerization process are added by supplement metering
Enter ethylene, control pressure is 2MPa.
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
89 grams of polymer are obtained, catalyst activity 8.9 × 106g/(molM·h).Polymeric properties are shown in Table 1.
Embodiment 8:
In 1L tank reactor, 2.6mol purification norbornene is added in the isoparG of 500ml, which is added
Enter into the reactor being purged with nitrogen in advance, Multi-step forming ethylene (2MPa) is saturated solution by ethylene, 120 DEG C,
2MPa and stirring under conditions of, sequentially add 12ml concentration be 1.0mol/L isobutyl aluminium alkoxide (i-BAO) solution, 10 μm of ol bis-
Phenyl methene (cyclopentadienyl group) (9- fluorenyl) zirconium dichloride, polymerization process are by supplementing metered ethylene, control pressure
1MPa。
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
65 grams of polymer are obtained, catalyst activity 6.5 × 106g/(molM·h).Polymeric properties are shown in Table 1.
Embodiment 9:
In 1L tank reactor, 2.6mol purification vinyl norbornene is added in the IsoparH of 500ml, by this
Solution is added in the reactor being purged with nitrogen in advance, and Multi-step forming ethylene (2MPa) is saturated solution by ethylene,
110 DEG C, 2MPa and stirring under conditions of, sequentially add 7ml concentration be 1.72mol/L methylaluminoxane (MAO) toluene solution,
10 μm of ol dimetylsilyls-bis--(1- indenyl) zirconium dichloride, polymerization process is by supplementing metered ethylene, control pressure
Power is 2MPa.
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
45 grams of polymer are obtained, catalyst activity 4.5 × 106g/(molM·h).Polymeric properties are shown in Table 1.
Embodiment 10:
In 1L tank reactor, 2.6mol purification vinyl norbornene is added in the IsoparJ of 500ml, by this
Solution is added in the reactor being purged with nitrogen in advance, and Multi-step forming ethylene (1MPa) is saturated solution by ethylene,
120 DEG C, 2MPa and stirring under conditions of, sequentially add 7ml concentration be 1.72mol/L methylaluminoxane (MAO) toluene solution,
10 μm of ol diphenyl methene (cyclopentadienyl group) (9- fluorenyl) zirconium dichlorides, polymerization process is by supplementing metered ethylene, control
Pressing pressure is 2MPa.
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
67 grams of polymer are obtained, catalyst activity 6.7 × 106g/(molM·h).Polymeric properties are shown in Table 1.
Embodiment 11:
In 1L tank reactor, 2.6mol purification vinyl norbornene is added in the IsoparE of 500ml, by this
Solution is added in the reactor being purged with nitrogen in advance, and Multi-step forming ethylene (2MPa) is saturated solution by ethylene, 80
DEG C, 2MPa and stirring under conditions of, sequentially add 16ml concentration be 1.5mol/L ethylaluminoxane (EAO) solution, 20 μm of ol bis-
Normal-butyl bis cyclopentadienyl zirconium dichloride, polymerization process are 2MPa by supplementing metered ethylene, control pressure.
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
31 grams of polymer are obtained, catalyst activity 3.1 × 106g/(molM·h).Polymeric properties are shown in Table 1.
Embodiment 12:
In 1L tank reactor, 5.2mol purification ethylidene norbornene is added in the IsoparC of 500ml, this is molten
Liquid is added in the reactor being purged with nitrogen in advance, and Multi-step forming ethylene (1MPa) is saturated solution by ethylene, 80
DEG C, 10MPa and stirring under conditions of, sequentially add 16ml concentration be 1.5mol/L modified methylaluminoxane (MMAO) solution, 20 μ
Mol di-n-butyl bis cyclopentadienyl zirconium dichloride, polymerization process are 1MPa by supplementing metered ethylene, control pressure.
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
36 grams of polymer are obtained, catalyst activity 3.6 × 106g/(molM·h).Polymeric properties are shown in Table 1.
Comparative example 1:
In 1L tank reactor, 0.65mol purification norbornene is dissolved in 500ml refined toluene wiring solution-forming, by this
Solution is added in the reactor being purged with nitrogen in advance, and Multi-step forming ethylene (1MPa) is saturated solution by ethylene,
Under conditions of 100 DEG C, 1MPa and stirring, it is molten to sequentially add the toluene that 14ml concentration is 1.72mol/L methylaluminoxane (MAO)
Liquid, 20 μm of ol isopropylidenes-(1- indenyl)-cyclopentadienyl zirconium dichloride, polymerization process is by supplementing metered ethylene, control
Pressing pressure is 1MPa.
After reacting 15min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
110 grams of polymer are obtained, catalyst activity 2.2 × 107g/(molM·h).Polymeric properties are shown in Table 1.
Comparative example 2:
In 1L tank reactor, 0.65mol purification norbornene is added in the hexamethylene of 500ml, which is added
Enter into the reactor being purged with nitrogen in advance, Multi-step forming ethylene (1MPa) is saturated solution by ethylene, 70 DEG C,
1MPa and stirring under conditions of, sequentially add 7ml concentration be 1.72mol/L methylaluminoxane (MAO) toluene solution, 10 μm of ol
Dimetylsilyl-is bis--(1- indenyl) zirconium dichloride, polymerization process is by supplementing metered ethylene, control pressure
1MPa。
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
37 grams of polymer are obtained, catalyst activity 7.4 × 106g/(molM·h).Polymeric properties are shown in Table 1.
Comparative example 3:
In 1L tank reactor, 1.3mol purification vinyl norbornene is dissolved in 500ml refined toluene wiring solution-forming,
The solution is added in the reactor being purged with nitrogen in advance, Multi-step forming ethylene (1MPa) is saturated solution by ethylene,
Under conditions of 100 DEG C, 1MPa and stirring, it is molten to sequentially add the toluene that 7ml concentration is 1.72mol/L methylaluminoxane (MAO)
Liquid, 10 μm of ol dimetylsilyls-bis--(1- indenyl) zirconium dichloride, polymerization process is by supplementing metered ethylene, control
Pressure is 1MPa.
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
89 grams of polymer are obtained, catalyst activity 1.78 × 107g/(molM·h).Polymeric properties are shown in Table 1.
Comparative example 4:
In 1L tank reactor, 1.3mol purification vinyl norbornene is added in 500ml n-hexane, by the solution
Be added in the reactor that was purged with nitrogen in advance, Multi-step forming ethylene (1MPa) is saturated solution by ethylene, 65 DEG C,
1MPa and stirring under conditions of, sequentially add 7ml concentration be 1.72mol/L methylaluminoxane (MAO) toluene solution, 10 μm of ol
Diphenyl methene (cyclopentadienyl group) (9- fluorenyl) zirconium dichloride, polymerization process control pressure by supplementing metered ethylene
For 1MPa.
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
37 grams of polymer are obtained, catalyst activity 7.4 × 106g/(molM·h).Polymeric properties are shown in Table 1.
Comparative example 5:
In 1L tank reactor, 2.6mol purification vinyl norbornene is dissolved in refined toluene wiring solution-forming, it will
The solution is added in the reactor being purged with nitrogen in advance, and Multi-step forming ethylene (1MPa) is saturated solution by ethylene,
Under conditions of 80 DEG C, 1MPa and stirring, sequentially adding 16ml concentration is 1.5mol/L modified methylaluminoxane (MMAO) solution, 20
μm ol di-n-butyl bis cyclopentadienyl zirconium dichloride, polymerization process are 1MPa by supplementing metered ethylene, control pressure.
After reacting 30min, stops reaction, reaction solution is poured into the ethyl alcohol containing 15% (v/v%) hydrochloric acid (by 150mL hydrochloric acid
With 1000mL ethyl alcohol form) in precipitating after filter, after filter cake wash with ethyl alcohol (2000ml), dry (60 DEG C of dryings to constant weight),
52 grams of polymer are obtained, catalyst activity 5.2 × 106g/(molM·h).Polymeric properties are shown in Table 1.
Comparative example 6:
The present embodiment uses 1L tank reactor.Purification norbornene 0.15mol is dissolved in 500ml refined toluene to match
At solution, which is added in the reactor being purged with nitrogen in advance, Multi-step forming ethylene (0.1MPa) makes solution quilt
Ethylene saturation, under conditions of 70 DEG C, 0.1MPa and stirring, sequentially adding 23.8ml concentration is 1.72mol/L methylaluminoxane
Toluene solution, 27.4 μm of ol 3,5- di-tert-butyl Salicylidene 2- propylthioaniline titanium trichloride single-site catalysts, polymerization
Process is 1bar by supplementing metered ethylene, control pressure.
After reacting 0.5h, stop reaction, reaction solution pour into containing 15% (v/v%) hydrochloric acid ethyl alcohol (by 150ml hydrochloric acid and
1000ml ethyl alcohol composition) in precipitating after filter, after filter cake wash with ethyl alcohol (300ml), dry (60 DEG C of dryings to constant weight), obtain poly-
25.7 grams of object are closed, catalyst activity 1.88 × 106g/(molM·h).Polymeric properties are shown in Table 1.
1 polymeric properties of table
* the polymer in comparative example 6 is homopolymerisation polyethylene
The above list is only a few specific embodiments of the present invention for finally, it should also be noted that.Obviously, this hair
Bright to be not limited to above embodiments, acceptable there are many deformations.Those skilled in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (10)
1. a kind of metallocene catalyst, which is characterized in that have chemical structure shown in formula 1 or formula 2:
In formula 1, R1 C1-C8Selected from linear or branched alkyl group, C13-C21Two arylalkyl groups, C1-C8Alkyl silyl, two aromatic radicals
In silicon substrate；Cyclopentadiene-R2 and cyclopentadiene-R3 be each independently selected from unsubstituted or substituted cyclopentadienyl group, fluorenyl or
Indenyl.
In formula 2, cyclopentadiene-R4 and cyclopentadiene-R5 are each independently selected from cyclopentadienyl group, fluorenyl or indenyl, R6 and R7
It is each independently selected from hydrogen, C1-C8Linear or branched alkyl group.
2. metallocene catalyst according to claim 1, which is characterized in that R1 C1-C4Linear or branched alkyl group, C13-
C17Two arylalkyl groups, C1-C4Alkyl silyl, C12-C16Two aromatic radical silicon substrates；R6 and R7 is hydrogen, C1-C4Linear chain or branched chain alkane
Base.
3. metallocene catalyst according to claim 1, which is characterized in that R1 is methyl, ethyl, isopropyl, diphenyl
Methyl, dimethyl silicon substrate, diphenyl silicon substrate.
4. metallocene catalyst according to claim 1, which is characterized in that the metallocene compound is selected from dimethyl
Silicyl-is bis--(1- indenyl) zirconium dichloride, isopropylidene (3- methyl cyclopentadienyl) (1- indenyl) zirconium dichloride, and diformazan
Base silicyl (cyclopentadienyl group) (1- indenyl) zirconium dichloride, diphenyl methene (cyclopentadienyl group) (9- fluorenyl) dichloride
Zirconium, isopropylidene (cyclopentadienyl group) (4,5- phendioxins-indenyl) zirconium dichloride, dimetylsilyl (cyclopentadienyl group)
(4,5- phendioxins-indenyl) zirconium dichloride.
5. a kind of method for preparing cyclic olefine copolymer using metallocene catalyst described in 4 any one of Claims 1-4,
It is characterized in that, reactor is added in isoparaffin, cycloolefin and ethylene, metallocene catalyst is added and a kind of co-catalyst carries out
Solution polymerization, polymerization reaction time 0.1-10h, reaction temperature is 40-95 DEG C, reaction pressure 0.1-5.0MPa.
6. according to the method described in claim 5, it is characterized in that, the molar ratio of the cycloolefin and ethylene be 1: 1~50: 1,
The molar ratio of the metallocene catalyst and cycloolefin is 1: 3000~1: 100000, and the molar ratio of the cycloolefin and ethylene is
2: 1~40: 1；The co-catalyst be methylaluminoxane (MAO), modification methylaluminoxane (MMAO), ethylaluminoxane
(EAO), isobutyl aluminium alkoxide (i-BAO), B (C6F5)3Or C (C6H5)3B(C6F5)3One or more of Deng；The co-catalysis
The molar ratio of agent and metallocene catalyst is 50: 1~5000: 1；The isoparaffin be IsoparC, IsoparE, IsoparG,
One of IsoparH, IsoparJ, IsoparK, IsoparL, IsoparM, IsoparN, IsoparP, IsoparV.
7. according to the method described in claim 5, it is characterized in that, the cycloolefin is norbornene, vinyl norbornene
One or more of with ethylidene norbornene.
8. according to the method described in claim 5, it is characterized in that, a kind of chain-transferring agent, the chain is added in the method
The molar ratio of transfer agent and the metallocene catalyst is 5-500: 1, wherein the chain-transferring agent is selected from trimethyl aluminium, triethyl group
Aluminium, tri-n-n-propyl aluminum, triisobutyl aluminium, three n-butylaluminums, triisopentyl aluminium, three n-pentyl aluminium, tri-n-hexyl aluminum, three isohesyls
Aluminium, diethylmethyl aluminium, dimethyl ethyl aluminium, a Chlorodimethyl aluminium, dichloro monomethyl aluminium, aluminium diethyl monochloride, one second of dichloro
Base aluminium, a chlorine diη-propyl aluminium, one n-propyl aluminium of dichloro, a chloro-di-isobutyl aluminum, one aluminium isobutyl of dichloro, a chlorine di-n-butyl
Aluminium, one n-butylaluminum of dichloro, a chlorine diisoamyl aluminium, one isopentyl aluminium of dichloro, a chlorine di-n-hexyl aluminium, one n-hexyl of dichloro
Aluminium, two isohesyl aluminium of a chlorine, one isohesyl aluminium of dichloro or their any combination.
9. according to the method described in claim 8, it is characterized in that, the chain-transferring agent is selected from trimethyl aluminium, triethyl aluminum, three
N-propyl aluminium, triisobutyl aluminium, aluminium diethyl monochloride, one aluminium ethide of dichloro or their any combination.
10. according to the method described in claim 8, it is characterized in that, the chain-transferring agent be selected from trimethyl aluminium, triethyl aluminum,
Triisobutyl aluminium or their any combination.
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