CN107200803B - A method of catalyst system and cycloolefin ring-opening polymerisation for cycloolefin ring-opening polymerisation - Google Patents
A method of catalyst system and cycloolefin ring-opening polymerisation for cycloolefin ring-opening polymerisation Download PDFInfo
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Abstract
The present invention relates to catalyst fields, and in particular, to a method of cycloolefin ring-opening polymerisation is carried out for the catalyst system of cycloolefin ring-opening polymerisation and using the catalyst system.The catalyst system has included the component A of major catalyst effect and the pre- ageing mixture for playing co-catalyst, and the pre- ageing mixture is by the way that the mixture of component B and component C to be aged to obtain；Wherein component A is MoCl5And/or WCl6；Component B is that chemical formula is AlR3And/or AlHR2Organo-aluminum compound, wherein R be C1-C6 alkyl；Component C is chlorohydrocarbon.The property of catalyst system of the invention is more stable, and cost is lower, for preferable conversion ratio to may be implemented when cycloolefin ring-opening polymerization and operate safer.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of catalyst system for cycloolefin ring-opening polymerisation and
The method for carrying out cycloolefin ring-opening polymerisation using the catalyst system.
Background technique
Ring-opening metathesis polymerization is a kind of important chemical reaction, can take this to synthesize various new high molecular material.In
In related fields research, the selection of catalyst and prepare the most key.The catalyst for being able to achieve ring-opening polymerisation has very much, substantially may be used
It is divided into four classes: (1) metal carbene catalyst.Also known as alkylene base class catalyst, the main metallic element of this kind of catalyst mainly have titanium,
Tungsten, molybdenum, four class of ruthenium.Wherein it is active it is highest be molybdenum class (Schrock catalyst) and ruthenium class (Grubbs catalyst).This kind of catalysis
Agent activity is high and stablizes, but synthesis step is more, and synthesis technology requires harsh therefore expensive.(2) metallocene catalyst.Cyclopentadienyl
Metal catalyst system is mainly made of metallocene (such as titanocenes) and Grignard Reagent or metal alkyls.This kind of catalyst is being opened
Research in terms of ring metathesis polymerization is less, and catalyst activity an order of magnitude lower than above-mentioned metal carbene catalyst.(3) water-soluble
Property catalyst.This kind of catalyst is mainly RuC13Hyrate.The catalyst can be catalyzed drop ice under the conditions of ethyl alcohol and water-soluble emulsion
Open loop sigmatropic reaction occurs for piece ene derivative, but this kind of catalyst usually activity is lower, therefore studies less.(4) Ziegler-is received
Type catalysts.The catalyst is usually bi-component catalyst system, the compound of the elements such as major catalyst W, Mo, Ru, Ti, such as
WCl6、WOCl4、SnR2H etc.；Co-catalyst is the metallo-organic compounds, such as AlR such as Al, Mg3、AlR2Cl、Al2R3Cl3Deng (R is
Methyl, ethyl or isobutyl group).The catalyst system biggest advantage being grouped as by these groups is low in cost, is suitble to extensive
Industrialized mass production.
In Ziegler-natta catalyst, the most commonly used major catalyst is MoCl5And WCl6, but main catalytic is only used only
Agent, cycloolefin ring-opening polymerisation is without activity, because must be added to co-catalyst.When alkyl aluminum substance is added, such as in MoCl5
AlEt is added3Binary catalyst is formed, when for dicyclopentadiene polymerization, the smell of gained dicyclopentadiene is very big, and explanation has
A large amount of unreacted monomers show that catalyst activity is very low.In order to solve this problem, and AlCl is added3To improve activity (referring to perhaps
Refined, Li Huaming, once sub- child, waited .MoC15-AlCl3-AlEt3It is catalyzed polymerization reaction research synthetic resin and the modeling of dicyclopentadiene
Material, 1997,14 (4): 22-24).When using chlorination alkyl aluminum class for co-catalyst, higher activity usually can be obtained, such as
WCl6/AlEt2Cl system (referring to Liu Pengsheng, Li Huaming dicyclopentadiene reaction injection molding plastics industry, 1993, (1):
31-38) and MoCl5/AlEt2Cl system (referring to Liu Hu, Yao great Hu, Ma Panpan, waits molybdenum base open loop displacement catalyst bicyclic
Pentadiene polymerization studies thermosetting resin, 2012,27 (5): 36-39).
However, chlorination alkyl aluminum (such as AlEt2Cl it is) the very active substance of a kind of property, easily reacts and lose with water
Effect, even minor amount of water present in air, chlorination alkyl aluminum can be reacted with it, and generate white cigarette, release big calorimetric, cause danger
Dangerous accident, therefore for industrial production, need stringent closed-loop operation.Meanwhile chlorination alkyl aluminum is also that a kind of price is more expensive
Substance, for industrial production, the shortcomings that there is catalyst higher costs.
Summary of the invention
The purpose of the present invention is overcome in existing cycloolefin ring-opening polymerization method to use chlorination alkyl aluminum as WCl6With/
Or MoCl5Co-catalyst when it is existing it is vulnerable, have the shortcomings that security risk, operation stringent and higher cost, provide one
Catalyst system of the kind for cycloolefin ring-opening polymerisation and the method using catalyst system progress cycloolefin ring-opening polymerisation.This hair
The property of bright catalyst system is more stable, and cost is lower, preferably turns for may be implemented when cycloolefin ring-opening polymerization
Rate and operate it is safer.
The present invention provides a kind of catalyst system, which has included the component A of major catalyst effect and has risen and help and urge
The pre- ageing mixture of agent effect, the pre- ageing mixture is by the way that the mixture of component B and component C to be aged to obtain；Its
Middle component A is MoCl5And/or WCl6；Component B is that chemical formula is AlR3And/or AlHR2Organo-aluminum compound, wherein R be C1-
The alkyl of C6；Component C is chlorohydrocarbon.
Invention additionally provides a kind of methods of cycloolefin ring-opening polymerisation, this method comprises: in the presence of an organic,
Cycloolefin monomers are added and catalyst system of the invention carries out polymerization reaction.
The present inventor has been surprisingly found that during further investigation, when using MoCl5And/or WCl6As main reminder
When agent carries out cycloolefin ring-opening polymerization, the mixture being aged with organo-aluminum compound and chlorohydrocarbon is existing to substitute
The conventional use of chlorination alkyl aluminum of technology can reach and the comparable conversion ratio of chlorination alkyl aluminum, while catalytic body of the invention
It is that property is more stable, cost is lower, and operates safer.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is 1 resulting polymers of embodiment1H-NMR spectrum.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of catalyst system, which has included the component A of major catalyst effect and has risen and help and urge
The pre- ageing mixture of agent effect, the pre- ageing mixture is by the way that the mixture of component B and component C to be aged to obtain；Its
Middle component A is MoCl5And/or WCl6；Component B is that chemical formula is AlR3And/or AlHR2Organo-aluminum compound, wherein R be C1-
The alkyl of C6；Component C is chlorohydrocarbon.
In the present invention, there is no particular limitation for the process and condition of the ageing, such as the process of the ageing can be with
It include: to contact component B and component C 0.5-5 hours at 30-80 DEG C；Preferably, by component B and component C at 40-60 DEG C
Contact 1-2 hours.
In the present invention, the proportion of three kinds of components does not limit explicitly, wherein the group in co-catalyst in terms of chlorine element
The molar ratio for dividing C and the component B in terms of aluminium element can be 1~10:1, preferably 3~6:1.Main catalyst component A is urged with helping
The proportion of agent component B and C can be carried out according to the major catalyst of this field routine and the proportion of co-catalyst, it is preferable that with
The component B of aluminium element meter with the molar ratio of the component A of elemental metal be 1~10:1, preferably 3~5:1.
In the present invention, the component B, that is, organo-aluminum compound is AlR3And/or AlHR2, wherein R is the alkyl of C1-C6,
The preferably alkyl of C2-C4, it is highly preferred that the organo-aluminum compound be selected from triethyl aluminum, tri-propyl aluminum, three n-butylaluminums,
Diethyl aluminium hydride, hydrogenation one of dibutyl aluminium and triisobutyl aluminium or a variety of.
In the present invention, the alkane that the component C, that is, chlorohydrocarbon is preferably selected from C1-C5 replaces gained by one or more Cl
Chlorohydrocarbon, C1-C5 alkene replace the alkane of resulting chlorohydrocarbon, C1-C5 by one or more Cl by one or more Cl
Replace the alkene of resulting chlorohydrocarbon and C1-C5 by one or more Cl and one or more benzene with one or more phenyl
Base replaces one of resulting chlorohydrocarbon or a variety of.The chlorohydrocarbon of the invention can use general formula CnHxClyPhzIt indicates,
In, Ph indicates phenyl, and arbitrary integer (such as 1,2,3,4,5) of the n in 1-5, the arbitrary integer being preferably selected from 2-4, y is selected from
Arbitrary integer (such as 1,2,3,4,5,6) in 1-6, the arbitrary integer being preferably selected from 1-4, arbitrary integer of the z in 0-5
(such as 0,1,2,3,4,5), the arbitrary integer being preferably selected from 0-3, and x+y+z=2n+2 or 2n.In addition to above-mentioned preferred model
It encloses, the range of n, y, z may be new range as composed by any two integer numerical value disclosed above, such as the model of n
Enclose may be 1-3,1-4,2-5 or 3-5.A kind of more preferably specific embodiment according to the present invention, the chlorohydrocarbon choosing
From one of 2- chloro-2-methyl propane, benzyl chloride, chlorallylene, triphenylchloromethane and trichloroethanes or a variety of.
Invention additionally provides a kind of methods of cycloolefin ring-opening polymerisation, wherein this method comprises: depositing in organic solvent
Under, cycloolefin monomers are added and catalyst system of the invention carries out polymerization reaction.
In the present invention, there is no particular limitation for the dosage of the catalyst system, as long as polymerization reaction can be made to occur,
For example, can be 1:0.8 × 10 with the molar ratio of cycloolefin monomers and catalyst system-4~10 × 10-4, preferably 1:2 × 10-4
~8 × 10-4, more preferably 1:4 × 10-4~5 × 10-4.The dosage of the catalyst system is with the metallic element in wherein component A
Meter.
In the present invention, there is no particular limitation for the type of the cycloolefin monomers, for example, can selected from dicyclopentadiene,
One of the derivative or a variety of of the derivative of dicyclopentadiene, norbornene and norbornene.
In the present invention, the general formula of the derivative of the norbornene and norbornene isWherein R1With
R2It is each independently selected from the alkyl and COOR of H, C1-C63, R3For the alkyl of H or C1-C6.When the cycloolefin monomers are drop ice
When piece alkene and/or the derivative of norbornene, polymerization reaction can be indicated with formula (1),
In the present invention, the general formula of the derivative of the dicyclopentadiene and dicyclopentadiene isIts
Middle R4And R5It is each independently selected from the alkyl and COOR of H, C1-C66, R6For the alkyl of H or C1-C6.When the cycloolefin monomers
When for the derivative of dicyclopentadiene and/or dicyclopentadiene, polymerization reaction can be indicated with formula (2),
In the present invention, the cycloolefin monomers, which can be individually added into, to be added in the form of wiring solution-forming, when with molten
When the form of liquid is added, there is no particular limitation for the concentration of solution, such as can be 0.01-5mol/L, preferably 0.5-2mol/
L。
In the present invention, the condition of the polymerization reaction can be carried out according to the conventional method of cycloolefin ring-opening polymerisation, example
It is 30-80 DEG C if the condition of the polymerization reaction may include: reaction temperature, the reaction time is 1-5 hours；It preferably includes: anti-
Answering temperature is 30-50 DEG C, and the reaction time is 3-5 hours.
In the present invention, the organic solvent is not particularly limited, as long as cycloolefin can be made to dissolve, is typically had
Solvent includes but is not limited to hexane, hexamethylene, heptane, pentane, isopentane, octane, hexahydrotoluene, benzene,toluene,xylene
With one of isopropylbenzene or a variety of.
In the present invention, after ring-opening polymerization completion, activity can be made using the method for addition terminator
Polymer chain loses activity, and achievees the purpose that terminate the copolymerization.The type and dosage of the terminator be not special
It limits, as long as the terminator can be such that polymer active chain inactivates.Generally, the terminator can be water, C1-C6
Aliphatic alcohol, C4-C12 aliphatic carboxylic acid and one of aryl polyol or a variety of, the aryl polyhydroxy
Compound refers to that at least there are two be optionally substituted by a hydroxyl group compound generated to the hydrogen atom on phenyl ring.Preferably, the terminator
For one of water, methanol, ethyl alcohol and isopropanol or a variety of.
In the present invention, in order to overcome oxygen to destroy catalyst active center, the ring-opening polymerization can be in inertia
It is carried out in atmosphere.The method for keeping inert atmosphere can be to be passed through inert gas after vacuumizing reaction vessel.The indifferent gas
Atmosphere for example can be nitrogen.
The method of cycloolefin ring-opening polymerisation of the invention further includes that solvent volatilizees to collect ring after polymerization reaction
Alkene ring-opening polymerization polymer product, in a conventional manner, details are not described herein for the mode of the solvent flashing.
In the present invention, the adding manner of the catalyst system can mix the pre- ageing of component A and component B and component C
It closes object to be separately added into, be together added after can also first mixing the pre- ageing mixture of component A and component B and component C, it is excellent
The pre- ageing mixture of component A and component B and component C is separately added by choosing.
In the present invention, component A, component B and component C can be used directly, can also be used in the form of wiring solution-forming.For
The solvent of component A, component B and component C are not particularly limited, as long as respective substance can be made to dissolve, typical solvent packet
Include but be not limited to hexane, hexamethylene, heptane, pentane, isopentane or octane, hexahydrotoluene, benzene,toluene,xylene and isopropyl
One of benzene is a variety of.For the solvent of polymerization, the solvent of dissolved constituent A, the solvent of dissolved constituent B and dissolved constituent C
Solvent may be the same or different.In the present invention, do not have to the component A of formation, the concentration of the organic solution of component B and component C
There is special restriction, such as the concentration of component solution A can be 0.01-1mol/L, the concentration of component B solution can be 0.01-
The concentration of 5mol/L and component C solution can be 0.01-10mol/L.
The present invention will be described in detail by way of examples below.
In the examples below, polymer1H-NMR spectrum is molten by German Bruker 400MHz nmr determination
Agent is deuterated chloroform.
Embodiment 1
Under nitrogen protection into 100ml vial, it is molten that the triisobutyl aluminium hexane that 23ml concentration is 0.2mol/L is added
Liquid and 1.5ml 2- chloro-2-methyl propane are aged 2 hours after mixing at 40 DEG C in advance, spare.Calculating chlorine/aluminium element molar ratio is
3.1。
Under nitrogen protection into 100ml vial, be added 50ml concentration be 1.2mol/L norbornene toluene solution,
0.5ml concentration is the MoCl of 0.06mol/L5Toluene solution and the above-mentioned pre- ageing mixture of 0.8ml, react at 30 DEG C after mixing
3 hours, ethyl alcohol is added and terminates reaction, obtains 4.6g polymer after solvent flashing.Calculate MoCl5It is with norbornene molar ratio
5.0×10-4, triisobutyl aluminium (in terms of aluminium element) and MoCl5The molar ratio of (in terms of Mo element) is 5.0, and polymerisation conversion is
81%.
Resulting polymers progress nuclear magnetic resonance is obtained1H-NMR spectrum as shown in Figure 1, from figure 1 it appears that being located at
At 5.3-5.5 peak integral area be located at 0.6-3.0 place peak integral area ratio be 1:4.1, represent in product in double bond
Hydrogen molar ratio on hydrogen and saturated carbon atom is 1:4.1, shows that polymer is norbornene open-loop polymeric reaction product, does not occur
Addition or cross-linking reaction.
Embodiment 2
Under nitrogen protection into 100ml vial, it is molten that the triisobutyl aluminium hexane that 20ml concentration is 0.2mol/L is added
Liquid and 2.7ml benzyl chloride are aged 1.5 hours after mixing at 50 DEG C in advance, spare.Calculating chlorine/aluminium element molar ratio is 5.9.
Under nitrogen protection into 100ml vial, be added 50ml concentration be 1.2mol/L norbornene toluene solution,
0.4ml concentration is the MoCl of 0.06mol/L5Toluene solution and the above-mentioned pre- ageing mixture of 0.4ml, react at 40 DEG C after mixing
3 hours, ethyl alcohol is added and terminates reaction, obtains 4.1g polymer after solvent flashing.Calculate MoCl5It is with norbornene molar ratio
4.0×10-4, triisobutyl aluminium (in terms of aluminium element) and MoCl5The molar ratio of (in terms of Mo element) is 3.0, and polymerisation conversion is
73%.
1H-NMR spectrum characterize polymer the result shows that, be located at 5.3-5.5 place's peak integral area and the peak at the 0.6-3.0
Integral area ratio is 1:4.0, and represent the hydrogen molar ratio on the hydrogen and saturated carbon atom in product in double bond is 1:4.0, table
Bright polymer is norbornene open-loop polymeric reaction product, and addition or cross-linking reaction do not occur.
Embodiment 3
Under nitrogen protection into 100ml vial, it is molten that the triisobutyl aluminium hexane that 20ml concentration is 0.2mol/L is added
Liquid and 1.5ml chlorallylene are aged 1.0 hours after mixing at 60 DEG C in advance, spare.Calculating chlorine/aluminium element molar ratio is 4.6.
Under nitrogen protection into 100ml vial, be added 50ml concentration be 1.2mol/L norbornene toluene solution,
0.4ml concentration is the MoCl of 0.06mol/L5Toluene solution and the above-mentioned pre- ageing mixture of 0.5ml, react at 40 DEG C after mixing
3 hours, ethyl alcohol is added and terminates reaction, obtains 4.4g polymer after solvent flashing.Calculate MoCl5It is with norbornene molar ratio
4.0×10-4, triisobutyl aluminium (in terms of aluminium element) and MoCl5The molar ratio of (in terms of Mo element) is 3.9, and polymerisation conversion is
78%.
1H-NMR spectrum characterize polymer the result shows that, be located at 5.3-5.5 place's peak integral area and the peak at the 0.6-3.0
Integral area ratio is 1:4.1, and represent the hydrogen molar ratio on the hydrogen and saturated carbon atom in product in double bond is 1:4.1, table
Bright polymer is norbornene open-loop polymeric reaction product, and addition or cross-linking reaction do not occur.
Embodiment 4
Under nitrogen protection into 100ml vial, the tri-propyl aluminum hexane solution that 0.5ml concentration is 0.2mol/L is added
The 2- chloro-2-methyl propane toluene solution for being 0.08mol/L with 4ml concentration is aged 1.0 hours after mixing at 50 DEG C in advance.Then
The norbornene toluene solution that 50ml concentration is 1.0mol/L and the MoCl that 0.4ml concentration is 0.06mol/L is added5Toluene is molten
Liquid reacts 3 hours at 40 DEG C after mixing, and ethyl alcohol is added and terminates reaction, obtains 3.8g polymer after solvent flashing.Calculating chlorine/
Aluminium element molar ratio is 3.2, MoCl5It is 4.8 × 10 with norbornene molar ratio-4, tri-propyl aluminum (in terms of aluminium element) and MoCl5
The molar ratio of (in terms of Mo element) is 4.2, polymerisation conversion 81%.
1H-NMR spectrum characterize polymer the result shows that, be located at 5.3-5.5 place's peak integral area and the peak at the 0.6-3.0
Integral area ratio is 1:4.0, and represent the hydrogen molar ratio on the hydrogen and saturated carbon atom in product in double bond is 1:4.0, table
Bright polymer is norbornene open-loop polymeric reaction product, and addition or cross-linking reaction do not occur.
Embodiment 5
Under nitrogen protection into 100ml vial, the hydrogenation dibutyl aluminium hexane that 22ml concentration is 0.2mol/L is added
Solution and 0.5ml 2- chloro-2-methyl propane are aged 5 hours after mixing at 30 DEG C in advance, spare.Calculate chlorine/aluminium element molar ratio
It is 1.1.
Under nitrogen protection into 100ml vial, be added 50ml concentration be 1.0mol/L norbornene toluene solution,
0.4ml concentration is the MoCl of 0.06mol/L5Toluene solution and the above-mentioned pre- ageing mixture of 1.2ml, react at 80 DEG C after mixing
3 hours, ethyl alcohol is added and terminates reaction, obtains 3.1g polymer after solvent flashing.Calculate MoCl5It is with norbornene molar ratio
4.8×10-4, hydrogenate dibutyl aluminium (in terms of aluminium element) and MoCl5The molar ratio of (in terms of Mo element) is 9.8, polymerisation conversion
It is 66%.
1H-NMR spectrum characterize polymer the result shows that, be located at 5.3-5.5 place's peak integral area and the peak at the 0.6-3.0
Integral area ratio is 1:3.9, and represent the hydrogen molar ratio on the hydrogen and saturated carbon atom in product in double bond is 1:3.9, table
Bright polymer is norbornene open-loop polymeric reaction product, and addition or cross-linking reaction do not occur.
Embodiment 6
Under nitrogen protection into 100ml vial, it is molten that the three n-butylaluminum hexanes that 22ml concentration is 0.2mol/L are added
Liquid and 4.5ml 2- chloro-2-methyl propane are aged 0.5 hour after mixing at 80 DEG C in advance, spare.Calculate chlorine/aluminium element molar ratio
It is 9.6.
Under nitrogen protection into 100ml vial, the norbornene derivative (R that 50ml concentration is 1.0mol/L is added1
And R2Respectively H and COOC (CH3)3) toluene solution, 0.4ml concentration be 0.06mol/L MoCl5Toluene solution and 0.15ml
Above-mentioned pre- ageing mixture reacts 5 hours at 30 DEG C after mixing, and ethyl alcohol is added and terminates reaction, obtains 2.4g after solvent flashing
Polymer.Calculate MoCl5It is 4.8 × 10 with norbornene molar ratio-4, three n-butylaluminums (in terms of aluminium element) and MoCl5(with Mo
Element meter) molar ratio be 1.0, polymerisation conversion 63%.
1H-NMR spectrum characterize polymer the result shows that, be located at 5.3-5.5 place's peak integral area and the peak at the 0.6-3.0
Integral area ratio is 1:4.1, and represent the hydrogen molar ratio on the hydrogen and saturated carbon atom in product in double bond is 1:4.1, table
Bright polymer is norbornene open-loop polymeric reaction product, and addition or cross-linking reaction do not occur.
Embodiment 7
Under nitrogen protection into 100ml vial, the diethyl aluminium hydride hexane that 23ml concentration is 0.2mol/L is added
Solution and 2.5ml 2- chloro-2-methyl propane are aged 2 hours after mixing at 40 DEG C in advance, spare.Calculate chlorine/aluminium element molar ratio
It is 5.1.
Under nitrogen protection into 100ml vial, be added 50ml concentration be 1.2mol/L norbornene toluene solution,
0.5ml concentration is the WCl of 0.06mol/L6Toluene solution and the above-mentioned pre- ageing mixture of 1.0ml, react 3 at 40 DEG C after mixing
Hour, ethyl alcohol is added and terminates reaction, obtains 4.0g polymer after solvent flashing.Calculate WCl6It is 5.0 with norbornene molar ratio
×10-4, diethyl aluminium hydride (in terms of aluminium element) and WCl6The molar ratio of (in terms of W element) is 6.0, and polymerisation conversion is
71%.
1H-NMR spectrum characterize polymer the result shows that, be located at 5.3-5.5 place's peak integral area and the peak at the 0.6-3.0
Integral area ratio is 1:4.0, and represent the hydrogen molar ratio on the hydrogen and saturated carbon atom in product in double bond is 1:4.0, table
Bright polymer is norbornene open-loop polymeric reaction product, and addition or cross-linking reaction do not occur.
Embodiment 8
Under nitrogen protection into 100ml vial, the triethyl aluminum hexane solution that 20ml concentration is 0.2mol/L is added
With 1.5ml 2- chloro-2-methyl propane, it is aged 1.5 hours in advance after mixing at 50 DEG C, it is spare.Calculating chlorine/aluminium element molar ratio is
3.5。
Under nitrogen protection into 100ml vial, it is molten that the dicyclopentadiene toluene that 40ml concentration is 1.5mol/L is added
Liquid, the MoCl that 0.5ml concentration is 0.06mol/L5Toluene solution and the above-mentioned pre- ageing mixture of 1.2ml, after mixing at 40 DEG C
Reaction 3 hours is added ethyl alcohol and terminates reaction, obtains 3.6g polymer after solvent flashing.Calculate MoCl5With dicyclopentadiene mole
Than being 5.0 × 10-4, triethyl aluminum (in terms of aluminium element) and MoCl5The molar ratio of (in terms of Mo element) is 7.4, polymerisation conversion
It is 60%.
Comparative example 1
Under nitrogen protection into 100ml vial, be added 50ml concentration be 1.2mol/L norbornene toluene solution,
0.5ml concentration is the MoCl of 0.06mol/L5Toluene solution and 0.3ml concentration are 0.5mol/L di-isobutyl aluminum chloride, after mixing
It is reacted 3 hours at 30 DEG C, ethyl alcohol is added and terminates reaction, obtains 4.8g polymer after solvent flashing.Calculate MoCl5With norborneol
Alkene molar ratio is 5.0 × 10-4, di-isobutyl aluminum chloride (in terms of aluminium element) and MoCl5(in terms of Mo element) molar ratio is 5.0,
Polymerisation conversion is 82%.
Comparative example 2
Under nitrogen protection into 100ml vial, be added 50ml concentration be 1.2mol/L norbornene toluene solution,
0.5ml concentration is the MoCl of 0.06mol/L5Toluene solution, the triisobutyl aluminium hexane solution that 0.75ml concentration is 0.2mol/L
The 2- chloro-2-methyl propane hexane solution for being 0.93mol/L with 0.5ml concentration, reacts 3 hours at 30 DEG C after mixing, is added
Ethyl alcohol terminates reaction, obtains 0.7g polymer after solvent flashing.Calculate 2- chloro-2-methyl propane in terms of chlorine element with aluminium member
The molar ratio of the triisobutyl aluminium of element meter is 3.1, MoCl5It is 5.0 × 10 with norbornene molar ratio-4, triisobutyl aluminium is (with aluminium
Element meter) and MoCl5(in terms of Mo element) molar ratio is 5.0, polymerisation conversion 12%.
By embodiment and the comparison of comparative example 1 as can be seen that catalyst system of the invention is used for cycloolefin ring-opening polymerisation
It may be implemented preferable in reaction or even can achieve and use the comparable catalytic effect of chlorination alkyl aluminum.By by embodiment 1
With the comparison of comparative example 2 as can be seen that of the invention handled to obtain pre- ageing mixture and individually make by component B and component C
Catalytic effect can be greatly improved by being compared with component B with component C.Meanwhile the application has used raw material cheap, that property is stable,
Resulting catalyst system property is stablized, and cost is relatively low, and operates safer.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.It is further to note that described in above-mentioned specific embodiment
Each particular technique feature can be combined in any appropriate way in the case of no contradiction, in order to avoid not
Necessary repetition, the invention will not be further described in various possible combinations.In addition, a variety of different implementations of the invention
Any combination can also be carried out between mode, as long as it does not violate the idea of the present invention, it is public equally to should be considered as institute of the invention
The content opened.
Claims (16)
1. a kind of catalyst system, which has included the component A of major catalyst effect and has played the pre- old of co-catalyst
Change mixture, the pre- ageing mixture is by the way that the mixture of component B and component C to be aged to obtain；Wherein component A is MoCl5
And/or WCl6；Component B is that chemical formula is AlR3And/or AlHR2Organo-aluminum compound, wherein R be C1-C6 alkyl；Component C
For chlorohydrocarbon；The process of the ageing includes: to contact component B and component C 0.5-5 hours at 30-80 DEG C.
2. catalyst system according to claim 1, wherein contact 1-2 hours component B and component C at 40-60 DEG C.
3. catalyst system according to claim 1, wherein the component C in terms of chlorine element is with the component B's in terms of aluminium element
Molar ratio is 1~10:1.
4. catalyst system according to claim 3, wherein the component C in terms of chlorine element is with the component B's in terms of aluminium element
Molar ratio is 3~6:1.
5. catalyst system according to claim 1, wherein the component B and component A with elemental metal in terms of aluminium element
Molar ratio be 1~10:1.
6. catalyst system according to claim 5, wherein the component B and component A with elemental metal in terms of aluminium element
Molar ratio be 3~5:1.
7. catalyst system described in any one of -6 according to claim 1, wherein the organo-aluminum compound is selected from triethyl group
Aluminium, tri-propyl aluminum, three n-butylaluminums, diethyl aluminium hydride, hydrogenation one of dibutyl aluminium and triisobutyl aluminium or a variety of.
8. catalyst system according to claim 7, wherein the alkane that the chlorohydrocarbon is selected from C1-C5 is one or more
Cl replaces the alkene of resulting chlorohydrocarbon, C1-C5 to replace the alkane of resulting chlorohydrocarbon, C1-C5 by one by one or more Cl
A or multiple Cl and one or more phenyl replace the alkene of resulting chlorohydrocarbon and C1-C5 by one or more Cl and one
A or multiple phenyl replace one of resulting chlorohydrocarbon or a variety of.
9. catalyst system according to claim 8, wherein the chlorohydrocarbon be selected from 2- chloro-2-methyl propane, benzyl chloride,
One of chlorallylene, triphenylchloromethane and trichloroethanes are a variety of.
10. a kind of method of cycloolefin ring-opening polymerisation, which is characterized in that this method comprises: in the presence of an organic, ring is added
Catalyst system described in any one of olefinic monomer and claim 1-9 carries out polymerization reaction.
11. according to the method described in claim 10, wherein, the cycloolefin monomers are urged with elemental metal in component A
The molar ratio of change system is 1:0.8 × 10-4~10 × 10-4。
12. according to the method for claim 11, wherein the cycloolefin monomers are urged with elemental metal in component A
The molar ratio of change system is 1:2 × 10-4~8 × 10-4。
13. method described in any one of 0-12 according to claim 1, wherein the cycloolefin monomers are selected from bicyclic penta 2
Alkene, the derivative of dicyclopentadiene, norbornene and norbornene one of derivative or a variety of.
14. according to the method for claim 13, wherein the general formula of the derivative of the norbornene and norbornene isWherein R1And R2It is each independently selected from the alkyl and COOR of H, C1-C63, R3For the alkyl of H or C1-C6.
15. according to the method for claim 13, wherein the general formula of the derivative of the dicyclopentadiene and dicyclopentadiene
ForWherein R4And R5It is each independently selected from the alkyl and COOR of H, C1-C66, R6For the alkyl of H or C1-C6.
16. according to the method described in claim 10, wherein, the condition of the polymerization reaction includes: that reaction temperature is 30-80
DEG C, the reaction time is 1-5 hours.
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