CN109593160A - A kind of preparation method of cyclic olefine copolymer - Google Patents
A kind of preparation method of cyclic olefine copolymer Download PDFInfo
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- CN109593160A CN109593160A CN201710928754.7A CN201710928754A CN109593160A CN 109593160 A CN109593160 A CN 109593160A CN 201710928754 A CN201710928754 A CN 201710928754A CN 109593160 A CN109593160 A CN 109593160A
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- 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
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- 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
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- 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
- C08F2420/05—Cp or analog where at least one of the carbon atoms of the coordinating ring is replaced by a heteroatom
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Abstract
The invention discloses a kind of preparation methods of cyclic olefine copolymer, belong to organic material field, and preparation step of the invention is that inert organic solvents, cycloolefin and ethylene are separately added into reactor under the conditions of temperature is 40-95 DEG C, pressure is 0.1-5.0MPa；Wherein the molar ratio of cycloolefin and ethylene is 1-50: 1；Then it is added or is added without chain-transferring agent；It is eventually adding catalyst and carries out solution polymerization, polymerization reaction time 0.1-10h.Polymerization activity prepared by the present invention is very high, and the ethylene-cycloolefin hydrocarbon copolymer that the ethylene-cycloolefin hydrocarbon copolymer of preparation is prepared relative to other catalyst systems has lower molecular weight.
Description
Technical field
The invention belongs to organic material fields, and in particular to a kind of to prepare cyclic olefine copolymer using metallocene catalyst
Method.
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.
Early stage cycloolefin copolymer is closed using Ziegler-Natta catalyst, and polymerization activity is lower.Metallocene catalyst
It is the efficient olefin polymerization catalysis developed in recent years, it can make alkene carry out stereoselective polymerization, can also be catalyzed ring
Olefinic polymerization and cycloolefin and ethylene copolymerization, to obtain a kind of novel thermoplastic.The copolymerization of ethylene and cycloolefin
Object has good optical transparence, low-birefringence, low water absorbable, high glass-transition temperature (Tg), high-intensitive, moisture resistance, resistance to
The characteristics such as high temperature, low-density, splendid dielectric strength and biocompatibility.Manufacture high density CD-ROM disk, optics lens,
The high-tech sectors such as optical fiber, capacitor film, medical devices are with a wide range of applications.
One kind non-metallocene catalyst involved in Chinese patent CN1887925, can be under the action of low dosage co-catalyst
High activity it is catalyzed the combined polymerization of the cycloolefins such as ethylene and cyclopentadiene, norbornene.Ethylene-obtained by the non-metallocene catalyst
Cyclic olefine copolymer is compared with general metallocene ethylene-cycloolefin hydrocarbon copolymer has higher intensity and modulus, this is greatly opened up
Its application space has been opened up, such as has had the occasion of particular/special requirement in orthostatic and well-pressed degree for packaging material.But and general cyclopentadienyl gold
Belong to ethylene-cycloolefin hydrocarbon copolymer to compare, the polymerization activity of the non-metallocene catalyst is relatively relatively low, and gained ethylene-cyclic olefin is total
Polymers tends to obtain heavy polymer, and easily forms gel, and processability is poor.
Summary of the invention
It is total that cycloolefin is prepared the purpose of the present invention is overcoming the deficiencies of the prior art and provide a kind of using metallocene catalyst
The method of polymers, thus obtained ethylene-cycloolefin hydrocarbon copolymer have unique excellent properties: high polymerization activity and low molecular weight
Or good processing performance.
A kind of method preparing cyclic olefine copolymer using metallocene catalyst provided by the invention is:
Under the conditions of temperature is 40-95 DEG C, pressure is 0.1-5.0MPa, by inert organic solvents, cycloolefin and ethylene point
It Jia Ru not reactor；Wherein the molar ratio of cycloolefin and ethylene is 1-50: 1；Then it is added or is added without chain-transferring agent；Finally plus
Enter catalyst and carries out solution polymerization, polymerization reaction time 0.1-10h；
The cycloolefin is any one or more of norbornene, vinyl norbornene or ethylidene norbornene；
Metallocene catalyst major catalyst as shown in formula 1 or formula 2.
In formula 1, R1 C1-C8Linear or branched alkyl group, C13-C21Two arylalkyl groups, C1-C8Alkyl silyl, two aromatic radicals
Silicon substrate, preferably C1-C4Linear or branched alkyl group, C13-C17Two arylalkyl groups, C1-C4Alkyl silyl, C12-C16Two aromatic radical silicon
Base, more preferable methyl, ethyl, isopropyl, diphenyl methyl, dimethyl silicon substrate, diphenyl silicon substrate；Cyclopentadiene-R2 and ring penta
Diene-R3 is 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
Hydrogen, C are each independently selected from R71-C8Linear or branched alkyl group, preferably hydrogen, C1-C4Linear or branched alkyl group.
In formula 3, group R1、R2、R3、R4, group R7 and group R9 can be the same or different, be each independently selected from
Hydrogen and C1-4Linear chain or branched chain alkyl；Group Y is O or S；Group A is S or O；Group R5Selected from hydrogen, C1-12Linear chain or branched chain alkyl,
C1-12Linear or branched alkyl group；Group R6With group R8Can be identical or different, it is each independently selected from hydrogen, C1-8Linear chain or branched chain
Alkyl；Group R10It is hydrogen or C1-6Linear chain or branched chain alkyl；M is selected from Ti or Zr；Group X is halogen, and n is selected from 2-3；SymbolRepresent singly-bound or double bond.
The catalyst further includes by methylaluminoxane (MAO), the methylaluminoxane (MMAO) of modification, ethylaluminoxane
(EAO), isobutyl aluminium alkoxide (i-BAO) or B (C6F5)3Deng one or more of be used as co-catalyst；
The molar ratio of the co-catalyst and the major catalyst is 50-5000: 1；
AlRpClq
Formula 4
The chain-transferring agent is selected from one or more of mixtures of structure shown in formula 4, and wherein R is C1-C10Alkyl, D
For 1-3, q 0-2.The molar ratio of chain-transferring agent and the major catalyst is 5-500: 1.
The metallocene catalyst as shown in Equation 1, R1Selected from C1-C4Linear or branched alkyl group, C13-C17Two aromatic radicals
Alkyl, C1-C4Alkyl silyl, C12-C16Two aromatic radical silicon substrates；
The metallocene catalyst as shown in Equation 2, wherein R6 and R7 is each independently selected from hydrogen, C1-C4Straight chain or branch
Alkyl group；
In formula 3, group R1、R2、R3、R4, group R7With group R9It can be the same or different, be each independently selected from
Hydrogen；Group Y is O；Group A is S；Group R5Selected from hydrogen；M is selected from Ti；Group X is chlorine.
The metallocene catalyst as shown in Equation 1, R1Selected from methyl, ethyl, isopropyl, diphenyl methyl, diformazan
Base silicon substrate, diphenyl silicon substrate；Cyclopentadiene-R12 and cyclopentadiene-R13It is each independently selected from unsubstituted or substituted ring penta 2
Alkenyl, fluorenyl or indenyl.
The molar ratio of the metallocene catalyst and cycloolefin is 1: 3000-100000, the cycloolefin and ethylene
Molar ratio is 2-40: 1.
The molar ratio of the chain-transferring agent and the major catalyst is 5-500: 1, wherein the chain-transferring agent is selected from three
Aluminium methyl (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), triisopentyl aluminium (Al (i-C5H11)3), three n-pentyl aluminium (Al (C5H11)3), three just
Hexyl aluminium (Al (C6H13)3), three isohesyl aluminium (Al (i-C6H13)3), diethylmethyl aluminium (Al (CH3)(CH3CH2)2), dimethyl
Aluminium ethide (Al (CH3CH2)(CH3)2), a Chlorodimethyl aluminium (Al (CH3)2Cl), dichloro monomethyl aluminium (Al (CH3)Cl2), a chlorine
Diethyl aluminum (Al (C2H5)2Cl), one aluminium ethide of dichloro (Al (C2H5)Cl2), a chlorine diη-propyl aluminium (Al (C3H7)2Cl), dichloro
One n-propyl aluminium (Al (C3H7)Cl2), a chloro-di-isobutyl 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 (Al (i-C of dichloro5H11)Cl2), a chlorine di-n-hexyl aluminium (Al (C6H13)2Cl), dichloro one
N-hexyl aluminium (Al (C6H13)Cl2), two isohesyl aluminium (Al (i-C of a chlorine6H13)2Cl), one isohesyl aluminium (Al (i-C of dichloro6H13)
Cl2) or their any combination.
The preferred trimethyl aluminium of the chain-transferring agent, triethyl aluminum, tri-n-n-propyl aluminum, triisobutyl aluminium, a chlorine diethyl
Aluminium, one aluminium ethide of dichloro or their any combination.
The preferred trimethyl aluminium of the chain-transferring agent, triethyl aluminum, triisobutyl aluminium or their any combination.
The inert organic solvents are straight chain aliphatic hydrocarbons, branched aliphatic hydrocarbons, substituted or unsubstituted cyclic aliphatic hydrocarbon, take
The mixture of generation or one or more of unsubstituted aromatic hydrocarbons.
The preferred hexane of the inert organic solvents, heptane, hexamethylene, cyclooctane, toluene, dimethylbenzene.
The metallocene catalyst further includes by methylaluminoxane (MAO), the methylaluminoxane (MMAO) of modification, aluminium ethide
Oxygen alkane (EAO), isobutyl aluminium alkoxide (i-BAO), B (C6F5)3Or C (C6H5)3B(C6F5)3Deng one or more of urge as helping
Agent；
The molar ratio of the co-catalyst and the major catalyst is 50-5000: 1；
The chain-transferring agent is selected from one or more of mixtures of structure shown in formula 4, and wherein R is C1-C10Alkyl, D
For 1-3, q 0-2.The molar ratio of the chain-transferring agent and major catalyst is 5-500: 1.
AlRpClq
Formula 4
The inert organic solvents are straight chain aliphatic hydrocarbons, branched aliphatic hydrocarbons, substituted or unsubstituted cyclic aliphatic hydrocarbon, substitution
Or the mixture of one or more of unsubstituted aromatic hydrocarbons.Straight chain aliphatic hydrocarbons can be hexane, heptane etc..Cyclic aliphatic hydrocarbon can
To be hexamethylene, cyclooctane etc..Aromatic hydrocarbons can be toluene, dimethylbenzene etc..
Polymerization reaction of the present invention can carry out in the tower or tank reactor with stirring, preferably still reaction
Device.Reactor volume is 0.05-1000L, preferably 0.1-100L.
A kind of method that cyclic olefine copolymer is prepared using metallocene catalyst provided by the invention, polymerization time with urge
The dosage of agent is related with reaction temperature, and the dosage of catalyst is more, and reaction temperature more high reaction rate is faster, and the reaction time gets over
It is short, generally 0.1-10h.
A kind of method preparing cyclic olefine copolymer using metallocene catalyst provided by the invention, can also pass through adjusting
The concentration control polymerization property of the chain-transferring agent and the molecular weight and structure of polymer.
A kind of preparation method being prepared cyclic olefine copolymer using metallocene catalyst provided by the invention can be used single poly-
Reactor assembly accomplished continuously or intermittently polymerization methods are closed, cyclic olefine copolymer is prepared in single-reactor.
Beneficial effect
The method provided according to the present invention, polymerization activity is very high, and the ethylene-cycloolefin hydrocarbon copolymer of preparation is urged relative to other
The ethylene-cycloolefin hydrocarbon copolymer of agent system preparation has lower molecular weight, under the same terms, when norbornene and ethylene list
Body is 5: 1, and catalyst concn is 4 × 10-5Mol/L, metallocene active are 5.37 × 106G/ (molh), metallocene COC molecule
Amount is 2.1 ten thousand, and non cyclopentadienyl catalyst activity is 1.78 × 107G/ (molh), non-cyclopentadienyl COC are 19.4 ten thousand, and metallocene COC has good
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 250ml glass reactor, 0.013mol purification norbornene is dissolved in 50ml 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 (0.1MPa) is saturated solution by ethylene,
Under conditions of 70 DEG C, 0.1MPa and stirring, sequentially adding 1.03ml concentration is 1.94mol/L modified methylaluminoxane (MMAO)
Hexahydrotoluene solution, bis- (4,5,6, the 7 tetrahydro -1- indenyl) zirconium dichlorides of 2 μm of ol rag- vinyl, control pressure be
0.1MPa。
After reacting 0.5h, stop reaction, by reaction solution pour into containing 15% (v/v%) hydrochloric acid ethyl alcohol (by 15mL hydrochloric acid and
100mL 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-
5.37 grams of object are closed, catalyst activity 5.37 × 106g/(mol·h).Polymeric properties are shown in Table 1.
Embodiment 2:
In 250ml glass reactor, 0.026mol purification norbornene is dissolved in 50ml 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 (0.1MPa) is saturated solution by ethylene,
Under conditions of 70 DEG C, 0.1MPa and stirring, sequentially adding 1.03ml concentration is 1.94mol/L modified methylaluminoxane (MMAO)
Hexahydrotoluene solution, bis- (4,5,6, the 7 tetrahydro -1- indenyl) zirconium dichlorides of 2 μm of ol rac- vinyl, control pressure be
0.1MPa。
After reacting 0.5h, stop reaction, by reaction solution pour into containing 15% (v/v%) hydrochloric acid ethyl alcohol (by 15mL hydrochloric acid and
100mL 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-
6.55 grams of object are closed, catalyst activity 6.55 × 106g/(mol·h).Polymeric properties are shown in Table 1.
Embodiment 3:
In 250ml glass reactor, 0.039mol purification norbornene is dissolved in 50ml 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 (0.1MPa) is saturated solution by ethylene,
Under conditions of 70 DEG C, 0.1MPa and stirring, sequentially adding 1.03ml concentration is 1.94mol/L modified methylaluminoxane (MMAO)
Hexahydrotoluene solution, 2 μm of ol dimetylsilyls-bis--(1- indenyl) zirconium dichloride, control pressure be 0.1MPa.
After reacting 0.5h, stop reaction, by reaction solution pour into containing 15% (v/v%) hydrochloric acid ethyl alcohol (by 15mL hydrochloric acid and
100mL 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-
5.79 grams of object are closed, catalyst activity 5.79 × 106g/(mol·h).Polymeric properties are shown in Table 1.
Embodiment 4:
In 250ml glass reactor, 0.052mol purification norbornene is dissolved in 50ml 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 (0.1MPa) is saturated solution by ethylene,
Under conditions of 70 DEG C, 0.1MPa and stirring, sequentially adding 1.03ml concentration is 1.94mol/L modified methylaluminoxane (MMAO)
Hexahydrotoluene solution, dimetylsilyl-it is bis--(1- indenyl) zirconium dichloride, control pressure be 0.1MPa.
After reacting 0.5h, stop reaction, by reaction solution pour into containing 15% (v/v%) hydrochloric acid ethyl alcohol (by 15mL hydrochloric acid and
100mL 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-
6.1 grams of object are closed, catalyst activity 6.10 × 106g/(mol.h).Polymeric properties are shown in Table 1.
Embodiment 5:
The present embodiment uses 1L tank reactor.0.325mol purification norbornene is dissolved in 500ml refined toluene
The solution is added in the reactor being purged with nitrogen in advance by wiring solution-forming, and Multi-step forming ethylene (5MPa) makes solution quilt
Ethylene saturation, under conditions of 80 DEG C, 5MPa and stirring, sequentially adding 13ml concentration is 1.55mol/L methylaluminoxane (MAO)
Solution, 21umol isopropylidene (cyclopentadiene) (1- indenyl) zirconium dichloride, control pressure are 5MPa.
After reacting 0.5h, stop reaction, by 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-
Close object 78g, catalyst activity 7.3 × 106g/(mol·h).Polymeric properties are shown in Table 1.
Embodiment 6:
The present embodiment uses 1L tank reactor.0.65mol purification norbornene 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 (10MPa) makes solution quilt
Ethylene saturation, under conditions of 80 DEG C, 10MPa and stirring, sequentially adding 13ml concentration is 1.55mol/L methylaluminoxane
(MAO) solution, 21 μm of ol dimetylsilyl (cyclopentadienyl group) (1- indenyl) zirconium dichlorides, control pressure are 10MPa.
After reacting 0.5h, stop reaction, by 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-
Close object 127g, catalyst activity 1.2 × 107g/(mol·h).Polymeric properties are shown in Table 1.
Embodiment 7:
The present embodiment uses 1L tank reactor.0.325mol purification norbornene is dissolved in 500ml refined toluene
The solution is added in the reactor being purged with nitrogen in advance by wiring solution-forming, and Multi-step forming ethylene (5MPa) makes solution quilt
Ethylene saturation, under conditions of 80 DEG C, 5MPa and stirring, sequentially adding 13ml concentration is 1.55mol/L methylaluminoxane (MAO)
Solution, 21 μm of ol diphenyl methene (cyclopentadienyl group) (9- fluorenyl) zirconium dichlorides, 1ml aluminium diethyl monochloride, control pressure are
5MPa。
After reacting 0.5h, stop reaction, by 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-
Close object 65g, catalyst activity 6.1 × 106g/(mol·h).Polymeric properties are shown in Table 1.
Embodiment 8:
The present embodiment uses 1L tank reactor.0.65mol purification norbornene 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 (10MPa) makes solution quilt
Ethylene saturation, under conditions of 80 DEG C, 10MPa and stirring, sequentially adding 13ml concentration is 1.55mol/L methylaluminoxane
(MAO) solution, 21 μm of ol isopropylidene (cyclopentadiene) (1- indenyl) zirconium dichlorides, 1ml aluminium diethyl monochloride, control pressure are
10MPa。
After reacting 0.5h, stop reaction, by 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-
Close object 101g, catalyst activity 9.5 × 106g/(mol·h).Polymeric properties are shown in Table 1.
Embodiment 9:
The present embodiment uses 1L tank reactor.0.325mol purification norbornene is dissolved in 500ml refined toluene
The solution is added in the reactor being purged with nitrogen in advance by wiring solution-forming, and Multi-step forming ethylene (5MPa) makes solution quilt
Ethylene saturation, under conditions of 60 DEG C, 5MPa and stirring, sequentially adding 13ml concentration is 1.5mol/L ethylaluminoxane (EAO)
Solution, 1ml triethyl aluminum, 2l μm of ol diphenyl methene (cyclopentadienyl group) (9- fluorenyl) zirconium dichloride, control pressure are 5MPa.
After reacting 0.5h, stop reaction, by 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-
Close object 90g, catalyst activity 8.4 × 106g/(mol·h).Polymeric properties are shown in Table 1.
Embodiment 10:
The present embodiment uses 1L tank reactor.0.65mol purification norbornene 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 (10MPa) makes solution quilt
Ethylene saturation, under conditions of 60 DEG C, 10MPa and stirring, sequentially adding 13ml concentration is 1.5mol/L ethylaluminoxane (EAO)
Solution, 1ml triethyl aluminum, dimetylsilyl (cyclopentadienyl group) (4,5- phendioxins-indenyl) zirconium dichloride control pressure
For 5MPa.
After reacting 0.5h, stop reaction, by 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-
Close object 125g, catalyst activity 1.2 × 107g/(mol·h).Polymeric properties are shown in Table 1.
Embodiment 11:
The present embodiment uses 1L tank reactor.0.325mol purification norbornene is dissolved in 500ml refined toluene
The solution is added in the reactor being purged with nitrogen in advance by wiring solution-forming, and Multi-step forming ethylene (5MPa) makes solution quilt
Ethylene saturation, under conditions of 60 DEG C, 5MPa and stirring, sequentially adding 10ml concentration is 2.05mol/L butyla-luminoxane (i-
BAO) solution, dimetylsilyl (cyclopentadienyl group) (4,5- phendioxins-indenyl) zirconium dichloride, control pressure are 5MPa.
After reacting 0.5h, stop reaction, by 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-
Close object 102g, catalyst activity 9.6 × 106g/(mol·h).Polymeric properties are shown in Table 1.
Embodiment 12:
The present embodiment uses 1L tank reactor.0.325mol purification norbornene is dissolved in 500ml refined toluene
The solution is added in the reactor being purged with nitrogen in advance by wiring solution-forming, and Multi-step forming ethylene (5MPa) makes solution quilt
Ethylene saturation, under conditions of 60 DEG C, 5MPa and stirring, sequentially adding 10ml concentration is 2.05mol/L butyla-luminoxane (i-
BAO) solution, 1ml triisobutyl aluminum solutions, 21 μm of ol isopropylidene (cyclopentadienyl group) (4,5- phendioxins-indenyl) dichlorides
Zirconium, control pressure are 5MPa.
After reacting 0.5h, stop reaction, by 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-
Close object 90.3g, catalyst activity 8.5 × 106g/(mol·h).Polymeric properties are shown in Table 1.
Embodiment 13:
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)
The triethyl aluminum polymerization process of liquid, 20 μm of ol isopropylidenes-(1- indenyl)-cyclopentadienyl zirconium dichloride, 1ml passes through supplement meter
Ethylene is added in amount, and control 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.
Embodiment 14:
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.
Embodiment 15:
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, sequentially adding 10.3ml concentration is 1.94mol/L modified methylaluminoxane (MMAO)
Hexahydrotoluene solution, 10 μm of ol dimetylsilyls-bis--(1- indenyl) zirconium dichloride, polymerization process by supplement meter
Ethylene is added in amount, and 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.
Embodiment 16:
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 1:
In 250ml glass reactor, 0.013mol purification norbornene is dissolved in 50ml 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 (0.1MPa) is saturated solution by ethylene,
Under conditions of 70 DEG C, 0.1MPa and stirring, sequentially adding 1.03ml concentration is 1.94mol/L modified methylaluminoxane (MMAO)
Hexahydrotoluene solution, 2 μm of ol 3- tert-butyl salicylidene 2- methyl mercapto aniline titanium trichloride, control pressure is
0.1MPa。
After reacting 0.5h, stop reaction, by reaction solution pour into containing 15% (v/v%) hydrochloric acid ethyl alcohol (by 15mL hydrochloric acid and
100mL 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-
1.76 grams of object are closed, catalyst activity 1.76 × 106g/(mol·h).Polymeric properties are shown in Table 1.
Comparative example 2:
The present embodiment uses 1L tank reactor.0.26mol purification norbornene 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 (0.2MPa) makes solution quilt
Ethylene saturation, under conditions of 70 DEG C, 0.2MPa and stirring, sequentially adding 10.3ml concentration is 1.94mol/L modified methyl aluminium
3, the 5- di-tert-butyl Salicylidene 2- propylthioaniline titanium trichloride of the hexahydrotoluene solution of oxygen alkane (MMAO), 20 μm of ol,
The triethyl aluminum of 1ml, control pressure are 0.2MPa.
After reacting 0.5h, stop reaction, by 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-
Close object 23.3g, catalyst activity 2.33 × 106g/(mol·h).Polymeric properties are shown in Table 1.
Comparative example 3:
In 250ml glass reactor, 0.013mol purification norbornene is dissolved in 50ml 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 (0.1MPa) is saturated solution by ethylene,
Under conditions of 70 DEG C, 0.1MPa and stirring, sequentially adding 1.03ml concentration is 1.94mol/L modified methylaluminoxane (MMAO)
Hexahydrotoluene solution, the di-n-butyl bis cyclopentadienyl zirconium dichloride of 2 μm of ol of 0.1ml triisobutyl aluminium, control pressure be 0.1MPa.
After reacting 0.5h, stop reaction, by reaction solution pour into containing 15% (v/v%) hydrochloric acid ethyl alcohol (by 15mL hydrochloric acid and
100mL 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-
0.85 gram of object is closed, catalyst activity 0.85 × 106g/(mol·h).Polymeric properties are shown in Table 1.
Comparative example 4:
The present embodiment uses 1L tank reactor.0.26mol purification norbornene 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 (5MPa) makes solution by second
Alkene saturation, under conditions of 70 DEG C, 5MPa and stirring, sequentially adding 10.3ml concentration is 1.94mol/L modified methylaluminoxane
(MMAO) hexahydrotoluene solution, 1ml triisobutyl aluminium, 20 μm of ol di-n-butyl bis cyclopentadienyl zirconium dichlorides, control pressure are 5MPa.
After reacting 0.5h, stop reaction, by 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-
Close object 15.2g, catalyst activity 1.52 × 106g/(mol·h).Polymeric properties are shown in Table 1.
1 polymeric properties of table
* the polymer in comparative example 5 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 preparation method of cyclic olefine copolymer, it is characterised in that: the following steps are included:
Under the conditions of temperature is 40-95 DEG C, pressure is 0.1-5.0MPa, inert organic solvents, cycloolefin and ethylene are added respectively
Enter reactor；Wherein the molar ratio of cycloolefin and ethylene is 1-50: 1；Then it is added or is added without chain-transferring agent；It is eventually adding and urges
Agent carries out solution polymerization, polymerization reaction time 0.1-10h；
The cycloolefin is any one or more of norbornene, vinyl norbornene or ethylidene norbornene；
Metallocene catalyst major catalyst as shown in formula 1 or formula 2.
In formula 1, R1 C1-C8Linear or branched alkyl group, C13-C21Two arylalkyl groups, C1-C8Alkyl silyl, two aromatic radical silicon
Base, preferably C1-C4Linear or branched alkyl group, C13-C17Two arylalkyl groups, C1-C4Alkyl silyl, C12-C16Two aromatic radical silicon substrates,
More preferable methyl, ethyl, isopropyl, diphenyl methyl, dimethyl silicon substrate, diphenyl silicon substrate；Cyclopentadiene-R2 and ring penta 2
Alkene-R3 is 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, preferably hydrogen, C1-C4Linear or branched alkyl group.
In formula 3, group R1、R2、R3、R4, group R7With group R9Can be the same or different, be each independently selected from hydrogen and
C1-4Linear chain or branched chain alkyl；Group Y is O or S；Group A is S or O；Group R5Selected from hydrogen, C1-12Linear chain or branched chain alkyl, C1-12
Linear or branched alkyl group；Group R6With group R8Can be identical or different, it is each independently selected from hydrogen, C1-8Linear chain or branched chain hydrocarbon
Base；Group R10It is hydrogen or C1-6Linear chain or branched chain alkyl；M is selected from Ti or Zr；Group X is halogen, and n is selected from 2-3；
The catalyst further include by methylaluminoxane (MAO), modification methylaluminoxane (MMAO), ethylaluminoxane (EAO),
Isobutyl aluminium alkoxide (i-BAO) or B (C6F5)3Deng one or more of be used as co-catalyst；
The molar ratio of the co-catalyst and the major catalyst is 50-5000: 1；
AlRpClq
4
The chain-transferring agent is selected from one or more of mixtures of structure shown in formula 4, and wherein R is C1-C10Alkyl, p 1-
3, q 0-2.The molar ratio of chain-transferring agent and the major catalyst is 5-500: 1.
2. preparation method according to claim 1, it is characterized in that: the metallocene catalyst as shown in Equation 1, R11Choosing
From C1-C4Linear or branched alkyl group, C13-C17Two arylalkyl groups, C1-C4Alkyl silyl, C12-C16Two aromatic radical silicon substrates；
The metallocene catalyst as shown in Equation 2, wherein R6 and R7 is each independently selected from hydrogen, C1-C4Linear chain or branched chain alkane
Base；
In formula 3, group R1、R2、R3、R4, group R7With group R9It can be the same or different, be each independently selected from hydrogen；Base
Group Y is O；Group A is S；Group R5Selected from hydrogen；M is selected from Ti；Group X is chlorine.Non-metallocene compound can specifically be enumerated: sub-
Salicyl 2- mercaptoaniline titanium trichloride, salicylidene 2- methyl mercapto aniline titanium trichloride, salicyl 2- methyl mercapto aniline trichlorine
Change titanium, salicylidene 2- propylthioaniline titanium trichloride, salicylidene 2- phenylsulfanyl aniline titanium trichloride, 3- tert-butyl Asia bigcatkin willow
Base 2- methyl mercapto aniline titanium trichloride, 3- tert-butyl salicylidene 2- propylthioaniline titanium trichloride, 3,5- di-t-butyl Asia water
Yankee 2- mercaptoaniline titanium trichloride, 3,5- di-tert-butyl Salicylidene 2- methyl mercapto aniline titanium trichloride, 3,5- di-t-butyl
Salicyl 2- methyl mercapto aniline titanium trichloride, 3,5- di-tert-butyl Salicylidene 2- propylthioaniline titanium trichloride, 3,5- bis- uncles
Butyl salicyl 2- propylthioaniline titanium trichloride etc., but it is not limited to this.
3. preparation method according to claim 2, it is characterized in that: the metallocene catalyst as shown in Equation 1, R11Choosing
From methyl, ethyl, isopropyl, diphenyl methyl, dimethyl silicon substrate, diphenyl silicon substrate；Cyclopentadiene-R12 and cyclopentadiene-R13
It is each independently selected from unsubstituted or substituted cyclopentadienyl group, fluorenyl or indenyl.
Metallocene compound can specifically be enumerated: dimetylsilyl-is bis--(1- indenyl) zirconium dichloride, and isopropylidene (3- first
Cyclopentadienyl group) (1- indenyl) zirconium dichloride, dimetylsilyl (cyclopentadienyl group) (1- indenyl) zirconium dichloride, hexichol
Base methene (cyclopentadienyl group) (9- fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl group) (4,5- phendioxins-indenyl) dichloro
Change zirconium, dimetylsilyl (cyclopentadienyl group) (4,5- phendioxins-indenyl) zirconium dichloride.
4. preparation method according to claim 1, it is characterized in that: the molar ratio of the metallocene catalyst and cycloolefin
It is 1: 3000-100000, the molar ratio of the cycloolefin and ethylene is 2-40: 1.
5. preparation method according to claim 1, it is characterized in that: mole of the chain-transferring agent and the major catalyst
Than being 5-500: 1, wherein the chain-transferring agent is selected from trimethyl aluminium (Al (CH3)3), triethyl aluminum (Al (CH2CH3)3), three positive third
Base aluminium (Al (C3H7)3), triisobutyl aluminium (Al (i-C4H9)3), three n-butylaluminums (Al (C4H9)3), triisopentyl 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), two
Ethyl-methyl aluminium (Al (CH3)(CH3CH2)2), dimethyl ethyl aluminium (Al (CH3CH2)(CH3)2), a Chlorodimethyl aluminium (Al
(CH3)2Cl), dichloro monomethyl aluminium (Al (CH3)Cl2), aluminium diethyl monochloride (Al (C2H5)2Cl), one aluminium ethide (Al of dichloro
(C2H5)Cl2), a chlorine diη-propyl aluminium (Al (C3H7)2Cl), one n-propyl aluminium (Al (C of dichloro3H7)Cl2), a chlorine diisobutyl
Aluminium (Al (i-C4H9)2Cl), one aluminium isobutyl of dichloro (Al (i-C4H9)Cl2), a chlorine di-n-butyl aluminium (Al (C4H9)2Cl), dichloro
One n-butylaluminum (Al (C4H9)Cl2), a chlorine diisoamyl aluminium (Al (i-C5H11)2Cl), one isopentyl aluminium (Al (i- of dichloro
C5H11)Cl2), a chlorine di-n-hexyl aluminium (Al (C6H13)2Cl), one n-hexyl aluminium (Al (C of dichloro6H13)Cl2), two isohesyl of a chlorine
Aluminium (Al (i-C6H13)2Cl), one isohesyl aluminium (Al (i-C of dichloro6H13)Cl2) or their any combination.
6. preparation method according to claim 5, it is characterized in that: the chain-transferring agent be trimethyl aluminium, triethyl aluminum,
Tri-n-n-propyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, one aluminium ethide of dichloro or their any combination.
7. preparation method according to claim 6, it is characterized in that: the chain-transferring agent is trimethyl aluminium, triethyl aluminum, three
Aluminium isobutyl or their any combination.
8. preparation method according to claim 1, it is characterized in that: the inert organic solvents are straight chain aliphatic hydrocarbons, branch
The mixture of one or more of chain aliphatic hydrocarbon, substituted or unsubstituted cyclic aliphatic hydrocarbon, substituted or unsubstituted aromatic hydrocarbons.
9. preparation method according to claim 8, it is characterized in that: the inert organic solvents are hexane, heptane, hexamethylene
Alkane, cyclooctane, toluene, dimethylbenzene.
10. preparation method according to claim 1, it is characterized in that: the polymerization reaction can with the tower of stirring or
It is carried out in tank reactor, reactor volume 0.05-1000L.
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| CN112812211A (en) * | 2021-02-08 | 2021-05-18 | 天津大学 | Polymerization method for efficiently regulating and controlling molecular weight of cycloolefin copolymer through reversible coordination chain transfer |
| CN112940183A (en) * | 2021-03-01 | 2021-06-11 | 扬州工业职业技术学院 | High-activity iron catalyst and application thereof in preparation of norbornene and ethylidene norbornene copolymer |
| CN114853947A (en) * | 2021-02-04 | 2022-08-05 | 中国石油天然气股份有限公司 | Composite catalyst and application thereof |
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