CN107200803A - A kind of method of catalyst system and catalyzing and cycloolefin ring-opening polymerisation for cycloolefin ring-opening polymerisation - Google Patents
A kind of method of catalyst system and catalyzing and cycloolefin ring-opening polymerisation for cycloolefin ring-opening polymerisation Download PDFInfo
- Publication number
- CN107200803A CN107200803A CN201610153501.2A CN201610153501A CN107200803A CN 107200803 A CN107200803 A CN 107200803A CN 201610153501 A CN201610153501 A CN 201610153501A CN 107200803 A CN107200803 A CN 107200803A
- Authority
- CN
- China
- Prior art keywords
- component
- catalyzing
- catalyst system
- catalyst
- aluminium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 *C1(*)C=CC2C1C1C=CCC2C1 Chemical compound *C1(*)C=CC2C1C1C=CCC2C1 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F132/00—Homopolymers 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
- C08F132/08—Homopolymers 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The present invention relates to catalyst field, in particular it relates to a kind of method that cycloolefin ring-opening polymerisation is carried out for the catalyst system and catalyzing of cycloolefin ring-opening polymerisation and using the catalyst system and catalyzing.The catalyst system and catalyzing has included the component A of major catalyst effect and has played the pre- ageing mixture of co-catalyst, and the pre- ageing mixture is by the way that component B and component C mixture ageing are obtained；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 the catalyst system and catalyzing of the present invention is more stablized, and cost is lower, and preferable conversion ratio can be realized during for cycloolefin ring-opening polymerization and is operated safer.
Description
Technical field
The present invention relates to catalyst field, in particular it relates to a kind of urging for cycloolefin ring-opening polymerisation
Change system and the method that cycloolefin ring-opening polymerisation is carried out using the catalyst system and catalyzing.
Background technology
Ring-opening metathesis polymerization is the important chemical reaction of a class, can take this to synthesize various new high score
Sub- material.In association area research, the selection of catalyst and prepare the most key.Open loop can be realized
The catalyst of polymerization has a lot, is broadly 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 has titanium, tungsten, molybdenum, the class of ruthenium four.Wherein
Active highest is molybdenum class (Schrock catalyst) and ruthenium class (Grubbs catalyst).This kind of catalysis
Agent activity is high and stably, but synthesis step is more, and synthesis technique requires harsh therefore expensive.(2)
Metallocene catalyst.Metallocene catalysis system is main by metallocene (such as titanocenes) and RMgBr or gold
Belong to alkylates composition.Research of this kind of catalyst in terms of ring-opening metathesis polymerization is less, and catalyst
Activity is than above-mentioned metal carbene catalyst order of magnitude lower.(3) water-soluble catalyst.This kind of catalysis
Agent is mainly RuC13Hyrate.The catalyst can be catalyzed norborneol under the conditions of ethanol and water-soluble emulsion
Ene derivative occur open loop sigmatropic reaction, but this kind of catalyst generally activity it is relatively low, therefore study compared with
It is few.(4) Ziegler-natta catalyst.The catalyst is usually bi-component catalyst system and catalyzing, main catalytic
Agent is the compound of the elements such as W, Mo, Ru, Ti, such as WCl6、WOCl4、SnR2H etc.；Help and urge
Agent is the metallo-organic compounds, such as AlR such as Al, Mg3、AlR2Cl、Al2R3Cl3Deng (R is first
Base, ethyl or isobutyl group).The catalyst system and catalyzing biggest advantage being made up of these components is that cost is low
It is honest and clean, it is adapted to heavy industrialization batch production.
In Ziegler-natta catalyst, the most commonly used major catalyst is MoCl5And WCl6, but only
Using only major catalyst, cycloolefin ring-opening polymerisation is without activity, because must be added to co-catalyst.When
When adding alkyl aluminum class material, such as in MoCl5Add AlEt3Binary catalyst is constituted, for bicyclic penta
During diene polymerization, the smell of gained dicyclopentadiene is very big, illustrates there are a large amount of unreacted monomers, shows
Catalyst activity is very low.In order to solve the problem, AlCl is added again3To improve activity (referring to perhaps refined, multitude
Huaming, once sub- child, waited .MoC15-AlCl3-AlEt3The polymerisation research for being catalyzed dicyclopentadiene is closed
Resin and plastics, 1997,14 (4):22-24).When using chlorination alkyl aluminum class for co-catalyst, lead to
Higher activity, such as WCl often can be obtained6/AlEt2Cl systems are (referring to Liu Pengsheng, Li Huaming bicyclic penta
Diene reaction injection molding plastics industries, 1993, (1):31-38) and MoCl5/AlEt2Cl systems are (referring to Liu
Tiger, Yao great Hu, horse Panpan waits the open loop of molybdenum bases to shift catalyst dicyclopentadiene polymerization studies thermosettings
Resin, 2012,27 (5):36-39).
However, chlorination alkyl aluminum (such as AlEt2Cl be) a class property very active material, easily with
Water is reacted and failed, even minor amount of water present in air, chlorination alkyl aluminum can be reacted,
White cigarette is produced, big calorimetric is released, triggers peril, therefore, it is necessary to tight for industrial production
Lattice closed-loop operation.Meanwhile, chlorination alkyl aluminum is also the expensive material of a class, for industrial production
For, have the shortcomings that catalyst cost is higher.
The content of the invention
The purpose of the present invention is to overcome in existing cycloolefin ring-opening polymerization method to make using chlorination alkyl aluminum
For WCl6And/or MoCl5Co-catalyst when exist easy failure, have potential safety hazard, operate strictly with
And the higher shortcoming of cost should there is provided a kind of catalyst system and catalyzing for cycloolefin ring-opening polymerisation and use
The method that catalyst system and catalyzing carries out cycloolefin ring-opening polymerisation.The property of the catalyst system and catalyzing of the present invention is more steady
Fixed, cost is lower, and preferable conversion ratio can be realized during for cycloolefin ring-opening polymerization and is grasped
Make safer.
The invention provides a kind of catalyst system and catalyzing, the catalyst system and catalyzing has included the component of major catalyst effect
A and the pre- ageing mixture for playing co-catalyst, the pre- mixture that is aged is by by component B and group
C mixture ageing is divided to obtain；Wherein component A is MoCl5And/or WCl6；Component B is chemistry
Formula is AlR3And/or AlHR2Organo-aluminum compound, wherein R be C1-C6 alkyl；Component C
For chlorohydrocarbon.
Invention additionally provides a kind of method of cycloolefin ring-opening polymerisation, this method includes：Organic
In the presence of solvent, the catalyst system and catalyzing for adding cycloolefin monomers and the present invention carries out polymerisation.
The present inventor has been surprisingly found that during further investigation, when using MoCl5And/or
WCl6When carrying out cycloolefin ring-opening polymerization as major catalyst, with organo-aluminum compound and chlorohydrocarbon
It is aged obtained mixture to substitute the conventional use of chlorination alkyl aluminum of prior art, can reaches and chlorine
Change the suitable conversion ratio of alkyl aluminum, while the catalyst system and catalyzing property of the present invention is more stablized, cost is more
It is low, and operate safer.
Other features and advantages of the present invention will give specifically in subsequent embodiment part
It is bright.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification,
It is used to explain the present invention together with following embodiment, but does not constitute the limit to the present invention
System.In the accompanying drawings：
Fig. 1 is the resulting polymers of embodiment 11H-NMR spectrum.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place
The embodiment of description is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of catalyst system and catalyzing, the catalyst system and catalyzing has included the component of major catalyst effect
A and the pre- ageing mixture for playing co-catalyst, the pre- mixture that is aged is by by component B and group
C mixture ageing is divided to obtain；Wherein component A is MoCl5And/or WCl6；Component B is chemistry
Formula is AlR3And/or AlHR2Organo-aluminum compound, wherein R be C1-C6 alkyl；Component C
For chlorohydrocarbon.
In the present invention, there is no particular limitation for the process and condition of the ageing, such as described ageing
Process can include：Component B and component C are contacted 0.5-5 hours at 30-80 DEG C；Preferably,
Component B and component C are contacted 1-2 hours at 40-60 DEG C.
In the present invention, the proportioning of three kinds of components is not limited clearly, wherein with chlorine in co-catalyst
The component C of the element meter and component B in terms of aluminium element mol ratio can be 1~10：1, be preferably
3~6：1.Main catalyst component A and cocatalyst component B and C proportioning can be normal according to this area
The proportioning of the major catalysts of rule and co-catalyst is carried out, it is preferable that component B in terms of aluminium element with
The component A of elemental metal mol ratio is 1~10：1, preferably 3~5：1.
In the present invention, the component B is that organo-aluminum compound is AlR3And/or AlHR2, wherein R
For C1-C6 alkyl, preferably C2-C4 alkyl, it is highly preferred that the organo-aluminum compound is selected
From triethyl aluminum, tri-propyl aluminum, three n-butylaluminums, diethyl aluminium hydride, hydrogenation dibutyl aluminium and three
One or more in aluminium isobutyl.
In the present invention, the component C is that chlorohydrocarbon is preferably selected from C1-C5 alkane by one or many
The alkene of chlorohydrocarbon, C1-C5 obtained by individual Cl substitution by one or more Cl replace obtained by chlorohydrocarbon,
C1-C5 alkane replaced by one or more Cl and one or more phenyl obtained by chlorohydrocarbon, and
C1-C5 alkene replaced by one or more Cl and one or more phenyl obtained by chlorohydrocarbon in one
Plant or a variety of.The chlorohydrocarbon of the present invention can use formula CnHxClyPhzRepresent, wherein, Ph tables
Show phenyl, arbitrary integers (such as 1,2,3,4,5) of the n in 1-5 is preferably selected from 2-4
Arbitrary integer, arbitrary integers (such as 1,2,3,4,5,6) of the y in 1-6, is preferably selected from 1-4
In arbitrary integer, arbitrary integers (such as 0,1,2,3,4,5) of the z in 0-5 be preferably selected from
Arbitrary integer in 0-3, and x+y+z=2n+2 or 2n.Except above-mentioned preferred scope, n, y, z
Scope can also be the new scope that is made up of any two integer numerical value disclosed above, such as n
Scope can also be 1-3,1-4,2-5 or 3-5.According to a kind of specific implementation being more highly preferred to of the present invention
Mode, the chlorohydrocarbon is selected from 2- chloro-2-methyls propane, benzyl chloride, chlorallylene, triphenylchloromethane
With the one or more in trichloroethanes.
Invention additionally provides a kind of method of cycloolefin ring-opening polymerisation, wherein, this method includes：
In the presence of an organic, the catalyst system and catalyzing for adding cycloolefin monomers and the present invention carries out polymerisation.
In the present invention, there is no particular limitation for the consumption of the catalyst system and catalyzing, as long as polymerization can be made anti-
Should occur, for example, can be for 1 with the mol ratio of cycloolefin monomers and catalyst system and catalyzing：0.8×
10-4~10 × 10-4, preferably 1：2×10-4~8 × 10-4, more preferably 1：4×10-4~5 × 10-4。
The consumption of the catalyst system and catalyzing is with the elemental metal in wherein component A.
In the present invention, there is no particular limitation for the species of the cycloolefin monomers, for example, can be selected from
One in dicyclopentadiene, the derivative of dicyclopentadiene, the derivative of ENB and ENB
Plant or a variety of.
In the present invention, the formula of the derivative of the ENB and ENB isWherein R1And R2It is each independently selected from H, C1-C6 alkyl and COOR3,
R3For H or C1-C6 alkyl.When the cycloolefin monomers are spreading out for ENB and/or ENB
Biochron, polymerisation can use formula (1) expression,
In the present invention, the formula of the derivative of the dicyclopentadiene and dicyclopentadiene isWherein R4And R5It is each independently selected from H, C1-C6 alkyl and COOR6,
R6For H or C1-C6 alkyl.When the cycloolefin monomers are dicyclopentadiene and/or dicyclopentadiene
Derivative when, polymerisation can with formula (2) represent,
In the present invention, the cycloolefin monomers can be individually added into can also the form of wiring solution-forming add
Enter, when adding as a solution, there is no particular limitation for the concentration of solution, for example, can be
0.01-5mol/L, preferably 0.5-2mol/L.
In the present invention, the condition of the polymerisation can according to cycloolefin ring-opening polymerisation routine side
Method is carried out, such as the condition of described polymerisation can include：Reaction temperature is 30-80 DEG C, during reaction
Between be 1-5 hours；Preferably include：Reaction temperature is 30-50 DEG C, and the reaction time is 3-5 hours.
In the present invention, the organic solvent has no particular limits, as long as can make cycloolefin dissolving i.e.
Can, typical organic solvent include but is not limited to hexane, hexamethylene, heptane, pentane, isopentane,
One or more in octane, hexahydrotoluene, benzene,toluene,xylene and isopropylbenzene.
In the present invention, can be using addition terminator after ring-opening polymerization completion
Method makes living polymer chains lose activity, and reaches the purpose for terminating the copolymerization.The end
Only the species and consumption of agent are not particularly limited, as long as the terminator can lose polymer active chain
Work.Usually, the terminator can be water, C1-C6 aliphatic alcohol, C4-C12 fat
One or more in aliphatic carboxylic acid and aryl polyol, the aryl polyol is
The hydrogen atom at least two referred on phenyl ring is optionally substituted by a hydroxyl group generated compound.Preferably, it is described
Terminator is the one or more in water, methanol, ethanol and isopropanol.
In the present invention, in order to overcome oxygen destroy catalyst active center, the ring-opening polymerization
It can carry out in an inert atmosphere.Keep the method for inert atmosphere can be for after reaction vessel is vacuumized
It is passed through inert gas.The inert atmosphere for example can be nitrogen.
The method of the cycloolefin ring-opening polymerisation of the present invention, which is additionally included in after polymerisation terminates, volatilizees solvent
To collect cycloolefin ring-opening polymerization polymer product, the mode of the solvent flashing in a conventional manner,
It will not be repeated here.
In the present invention, the feed postition of the catalyst system and catalyzing can be by component A and component B and component C
Pre- ageing mixture be separately added into, can also be first by component A and component B and component C pre- ageing
Mixture is another with adding after mixing, and preferably mixes component A and component B and component C pre- ageing
Compound is separately added into.
In the present invention, component A, component B and component C can be used directly, can also be made into molten
Liquid form is used.Solvent for component A, component B and component C has no particular limits, as long as
Can make respective substance dissolve, typical solvent include but is not limited to hexane, hexamethylene, heptane,
Pentane, isopentane or, one in octane, hexahydrotoluene, benzene,toluene,xylene and isopropylbenzene
Plant or a variety of.Solvent, dissolved constituent A solvent, dissolved constituent B solvent for polymerization and molten
The solvent for solving component C can be with identical, can also be different.In the present invention, component A, component to formation
There is no particular limitation for the concentration of B and component C organic solution, and the concentration of such as component solution A can
Think 0.01-1mol/L, the concentration of component B solution can be 0.01-5mol/L, and component C solution
Concentration 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 total to by German Bruker 400MHz nuclear-magnetisms
Vibration Meter is determined, and solvent is deuterochloroform.
Embodiment 1
Under nitrogen protection into 100ml vials, three isobutyls that 23ml concentration is 0.2mol/L are added
Base aluminium hexane solution and 1.5ml 2- chloro-2-methyl propane, are aged 2 hours in advance after mixing at 40 DEG C, standby
With.It is 3.1 to calculate chlorine/aluminium element mol ratio.
Under nitrogen protection into 100ml vials, the norborneol that 50ml concentration is 1.2mol/L is added
Alkene toluene solution, 0.5ml concentration are 0.06mol/L MoCl5Toluene solution and the above-mentioned pre- ageings of 0.8ml
Mixture, reacts 3 hours after mixing at 30 DEG C, adds after ethanol terminating reaction, solvent flashing and obtains
To 4.6g polymer.Calculate MoCl5It is 5.0 × 10 with ENB mol ratio-4, triisobutyl aluminium (with
Aluminium element meter) and MoCl5The mol ratio of (being counted using Mo elements) is 5.0, and polymerisation conversion is 81%.
Resulting polymers progress nuclear magnetic resonance is obtained1H-NMR spectrum as shown in Figure 1, can from Fig. 1
It is 1 positioned at peak integral area at 5.3-5.5 and positioned at peak integral area ratio at 0.6-3.0 to find out：
4.1, it is 1 to represent the hydrogen mol ratio on the hydrogen and saturated carbon atom in product in double bond：4.1, show
Polymer is norbornene open-loop polymeric reaction product, and addition or cross-linking reaction do not occur.
Embodiment 2
Under nitrogen protection into 100ml vials, three isobutyls that 20ml concentration is 0.2mol/L are added
Base aluminium hexane solution and 2.7ml benzyl chlorides, are aged 1.5 hours in advance after mixing at 50 DEG C, standby.Calculate
Chlorine/aluminium element mol ratio is 5.9.
Under nitrogen protection into 100ml vials, the norborneol that 50ml concentration is 1.2mol/L is added
Alkene toluene solution, 0.4ml concentration are 0.06mol/L MoCl5Toluene solution and the above-mentioned pre- ageings of 0.4ml
Mixture, reacts 3 hours after mixing at 40 DEG C, adds after ethanol terminating reaction, solvent flashing and obtains
To 4.1g polymer.Calculate MoCl5It is 4.0 × 10 with ENB mol ratio-4, triisobutyl aluminium (with
Aluminium element meter) and MoCl5The mol ratio of (being counted using Mo elements) is 3.0, and polymerisation conversion is 73%.
1H-NMR spectrum characterizes polymer result and shows that peak integral area is with being located at 5.3-5.5
Integral area ratio in peak is 1 at 0.6-3.0：4.0, the hydrogen and saturated carbon that represent in product in double bond are former
Hydrogen mol ratio on son is 1：4.0, it is norbornene open-loop polymeric reaction product to show polymer, not
Generation addition or cross-linking reaction.
Embodiment 3
Under nitrogen protection into 100ml vials, three isobutyls that 20ml concentration is 0.2mol/L are added
Base aluminium hexane solution and 1.5ml chlorallylenes, are aged 1.0 hours in advance after mixing at 60 DEG C, standby.Meter
It is 4.6 to calculate chlorine/aluminium element mol ratio.
Under nitrogen protection into 100ml vials, the norborneol that 50ml concentration is 1.2mol/L is added
Alkene toluene solution, 0.4ml concentration are 0.06mol/L MoCl5Toluene solution and the above-mentioned pre- ageings of 0.5ml
Mixture, reacts 3 hours after mixing at 40 DEG C, adds after ethanol terminating reaction, solvent flashing and obtains
To 4.4g polymer.Calculate MoCl5It is 4.0 × 10 with ENB mol ratio-4, triisobutyl aluminium (with
Aluminium element meter) and MoCl5The mol ratio of (being counted using Mo elements) is 3.9, and polymerisation conversion is 78%.
1H-NMR spectrum characterizes polymer result and shows that peak integral area is with being located at 5.3-5.5
Integral area ratio in peak is 1 at 0.6-3.0：4.1, the hydrogen and saturated carbon that represent in product in double bond are former
Hydrogen mol ratio on son is 1：4.1, it is norbornene open-loop polymeric reaction product to show polymer, not
Generation addition or cross-linking reaction.
Embodiment 4
Under nitrogen protection into 100ml vials, the tripropyl that 0.5ml concentration is 0.2mol/L is added
Aluminium hexane solution and 4ml concentration are 0.08mol/L 2- chloro-2-methyl propane toluene solutions, after mixing
50 DEG C are aged 1.0 hours in advance.Then the ENB toluene solution that 50ml concentration is 1.0mol/L is added
With the MoCl that 0.4ml concentration is 0.06mol/L5Toluene solution, reacts 3 hours after mixing at 40 DEG C,
3.8g polymer is obtained after adding ethanol terminating reaction, solvent flashing.Calculating chlorine/aluminium element mol ratio is
3.2, MoCl5It is 4.8 × 10 with ENB mol ratio-4, tri-propyl aluminum (in terms of aluminium element) and MoCl5
The mol ratio of (being counted using Mo elements) is 4.2, and polymerisation conversion is 81%.
1H-NMR spectrum characterizes polymer result and shows that peak integral area is with being located at 5.3-5.5
Integral area ratio in peak is 1 at 0.6-3.0：4.0, the hydrogen and saturated carbon that represent in product in double bond are former
Hydrogen mol ratio on son is 1：4.0, it is norbornene open-loop polymeric reaction product to show polymer, not
Generation addition or cross-linking reaction.
Embodiment 5
Under nitrogen protection into 100ml vials, the hydrogenation two that 22ml concentration is 0.2mol/L is added
Butyl aluminium hexane solution and 0.5ml 2- chloro-2-methyl propane, are aged 5 hours in advance after mixing at 30 DEG C, standby
With.It is 1.1 to calculate chlorine/aluminium element mol ratio.
Under nitrogen protection into 100ml vials, the norborneol that 50ml concentration is 1.0mol/L is added
Alkene toluene solution, 0.4ml concentration are 0.06mol/L MoCl5Toluene solution and the above-mentioned pre- ageings of 1.2ml
Mixture, reacts 3 hours after mixing at 80 DEG C, adds after ethanol terminating reaction, solvent flashing and obtains
To 3.1g polymer.Calculate MoCl5It is 4.8 × 10 with ENB mol ratio-4, hydrogenate dibutyl aluminium
(in terms of aluminium element) and MoCl5The mol ratio of (being counted using Mo elements) is 9.8, and polymerisation conversion is
66%.
1H-NMR spectrum characterizes polymer result and shows that peak integral area is with being located at 5.3-5.5
Integral area ratio in peak is 1 at 0.6-3.0：3.9, the hydrogen and saturated carbon that represent in product in double bond are former
Hydrogen mol ratio on son is 1：3.9, it is norbornene open-loop polymeric reaction product to show polymer, not
Generation addition or cross-linking reaction.
Embodiment 6
Under nitrogen protection into 100ml vials, the three positive fourths that 22ml concentration is 0.2mol/L are added
Base aluminium hexane solution and 4.5ml 2- chloro-2-methyl propane, are aged 0.5 hour in advance after mixing at 80 DEG C, standby
With.It is 9.6 to calculate chlorine/aluminium element mol ratio.
Under nitrogen protection into 100ml vials, the norborneol that 50ml concentration is 1.0mol/L is added
Ene derivative (R1And R2Respectively H and COOC (CH3)3) toluene solution, 0.4ml concentration be
0.06mol/L MoCl5Toluene solution and the above-mentioned pre- ageing mixtures of 0.15ml, after mixing at 30 DEG C
Reaction 5 hours, 2.4g polymer is obtained after adding ethanol terminating reaction, solvent flashing.Calculate MoCl5
It is 4.8 × 10 with ENB mol ratio-4, three n-butylaluminums (in terms of aluminium element) and MoCl5(with
Mo elements meter) mol ratio be 1.0, polymerisation conversion is 63%.
1H-NMR spectrum characterizes polymer result and shows that peak integral area is with being located at 5.3-5.5
Integral area ratio in peak is 1 at 0.6-3.0：4.1, the hydrogen and saturated carbon that represent in product in double bond are former
Hydrogen mol ratio on son is 1：4.1, it is norbornene open-loop polymeric reaction product to show polymer, not
Generation addition or cross-linking reaction.
Embodiment 7
Under nitrogen protection into 100ml vials, the hydrogenation two that 23ml concentration is 0.2mol/L is added
Aluminium ethide hexane solution and 2.5ml 2- chloro-2-methyl propane, are aged 2 hours in advance after mixing at 40 DEG C, standby
With.It is 5.1 to calculate chlorine/aluminium element mol ratio.
Under nitrogen protection into 100ml vials, the norborneol that 50ml concentration is 1.2mol/L is added
Alkene toluene solution, 0.5ml concentration are 0.06mol/L WCl6Toluene solution and the above-mentioned pre- ageings of 1.0ml
Mixture, reacts 3 hours after mixing at 40 DEG C, adds after ethanol terminating reaction, solvent flashing and obtains
To 4.0g polymer.Calculate WCl6It is 5.0 × 10 with ENB mol ratio-4, diethyl aluminium hydride
(in terms of aluminium element) and WCl6The mol ratio of (being counted using W elements) is 6.0, and polymerisation conversion is 71%.
1H-NMR spectrum characterizes polymer result and shows that peak integral area is with being located at 5.3-5.5
Integral area ratio in peak is 1 at 0.6-3.0：4.0, the hydrogen and saturated carbon that represent in product in double bond are former
Hydrogen mol ratio on son is 1：4.0, it is norbornene open-loop polymeric reaction product to show polymer, not
Generation addition or cross-linking reaction.
Embodiment 8
Under nitrogen protection into 100ml vials, the triethyl group that 20ml concentration is 0.2mol/L is added
Aluminium hexane solution and 1.5ml 2- chloro-2-methyl propane, are aged 1.5 hours in advance after mixing at 50 DEG C, standby
With.It is 3.5 to calculate chlorine/aluminium element mol ratio.
Under nitrogen protection into 100ml vials, it is bicyclic the penta of 1.5mol/L to add 40ml concentration
Diene toluene solution, 0.5ml concentration are 0.06mol/L MoCl5Toluene solution and 1.2ml are above-mentioned pre- old
Change mixture, reacted 3 hours at 40 DEG C after mixing, added after ethanol terminating reaction, solvent flashing
Obtain 3.6g polymer.Calculate MoCl5It is 5.0 × 10 with dicyclopentadiene molar ratio-4, triethyl aluminum
(in terms of aluminium element) and MoCl5The mol ratio of (being counted using Mo elements) is 7.4, and polymerisation conversion is
60%.
Comparative example 1
Under nitrogen protection into 100ml vials, the norborneol that 50ml concentration is 1.2mol/L is added
Alkene toluene solution, 0.5ml concentration are 0.06mol/L MoCl5Toluene solution and 0.3ml concentration are
0.5mol/L di-isobutyl aluminum chlorides, react 3 hours after mixing at 30 DEG C, add ethanol and terminate instead
Should, 4.8g polymer is obtained after solvent flashing.Calculate MoCl5With ENB mol ratio be 5.0 ×
10-4, di-isobutyl aluminum chloride (in terms of aluminium element) and MoCl5(in terms of Mo elements) mol ratio is
5.0, polymerisation conversion is 82%.
Comparative example 2
Under nitrogen protection into 100ml vials, the norborneol that 50ml concentration is 1.2mol/L is added
Alkene toluene solution, 0.5ml concentration are 0.06mol/L MoCl5Toluene solution, 0.75ml concentration are
0.2mol/L triisobutyl aluminium hexane solution and 0.5ml concentration is 0.93mol/L 2- chloro-2-methyls third
Alkane hexane solution, reacts 3 hours after mixing at 30 DEG C, adds ethanol terminating reaction, solvent flashing
After obtain 0.7g polymer.Calculate the 2- chloro-2-methyls propane in terms of chlorine element and three in terms of aluminium element
The mol ratio of aluminium isobutyl is 3.1, MoCl5It is 5.0 × 10 with ENB mol ratio-4, triisobutyl
Aluminium (in terms of aluminium element) and MoCl5(being counted using Mo elements) mol ratio is 5.0, and polymerisation conversion is
12%.
Contrasted by embodiment and comparative example 1 as can be seen that the catalyst system and catalyzing of the present invention is used for into cycloolefin
It can realize preferably or even can reach in ring-opening polymerization and be urged with using chlorination alkyl aluminum is suitable
Change effect.By embodiment 1 and comparative example 2 are contrasted as can be seen that the present invention by component B and group
Point C progress handle obtain pre- ageing mixture can be significantly compared with component B and component C is used alone
Improve catalytic effect.Meanwhile, the application used inexpensively, the stable raw material of property, the catalysis of gained
Agent system property is stable, and cost is relatively low, and operates safer.
The preferred embodiment of the present invention described in detail above, still, the present invention is not limited to above-mentioned
Detail in embodiment, can be to skill of the invention in the range of the technology design of the present invention
Art scheme carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.In addition
It should be noted that each particular technique feature described in above-mentioned embodiment, not
In the case of contradiction, it can be combined by any suitable means, in order to avoid unnecessary weight
Multiple, the present invention no longer separately illustrates to various possible combinations.In addition, the present invention it is various not
With embodiment between can also be combined, as long as its without prejudice to the present invention thought, its
Content disclosed in this invention should be equally considered as.
Claims (11)
1. a kind of catalyst system and catalyzing, the catalyst system and catalyzing has included the component A of major catalyst effect and has risen to help to urge
The pre- ageing mixture of agent effect, the pre- ageing mixture passes through mixing component B and component C
Compound ageing is obtained；Wherein component A is MoCl5And/or WCl6；Component B is that chemical formula is AlR3
And/or AlHR2Organo-aluminum compound, wherein R be C1-C6 alkyl；Component C is chlorohydrocarbon.
2. catalyst system and catalyzing according to claim 1, wherein, the process of the ageing includes：Will
Component B and component C are contacted 0.5-5 hours at 30-80 DEG C；Preferably, by component B and component C
Contacted 1-2 hours at 40-60 DEG C.
3. catalyst system and catalyzing according to claim 1, wherein, component C in terms of chlorine element with
The component B of aluminium element meter mol ratio is 1~10：1, preferably 3~6：1.
4. catalyst system and catalyzing according to claim 1, wherein, component B in terms of aluminium element with
The component A of elemental metal mol ratio is 1~10：1, preferably 3~5：1.
5. the catalyst system and catalyzing according to any one in claim 1-4, wherein, the organo-aluminium
Compound is selected from triethyl aluminum, tri-propyl aluminum, three n-butylaluminums, diethyl aluminium hydride, two fourths of hydrogenation
One or more in base aluminium and triisobutyl aluminium；
Preferably, the chlorohydrocarbon be selected from C1-C5 alkane replaced by one or more Cl obtained by chlorine
For hydrocarbon, C1-C5 alkene by one or more Cl replace obtained by chlorohydrocarbon, C1-C5 alkane by one
Chlorohydrocarbon obtained by individual or multiple Cl and one or more phenyl substitution, and C1-C5 alkene by one
The one or more in chlorohydrocarbon obtained by individual or multiple Cl and one or more phenyl substitutions；
It is highly preferred that the chlorohydrocarbon is selected from 2- chloro-2-methyls propane, benzyl chloride, chlorallylene, triphen
One or more in base chloromethanes and trichloroethanes.
6. a kind of method of cycloolefin ring-opening polymerisation, it is characterised in that this method includes：Organic molten
In the presence of agent, add the catalyst system and catalyzing in cycloolefin monomers and claim 1-5 described in any one and carry out
Polymerisation.
7. method according to claim 6, wherein, the cycloolefin monomers with component A
The mol ratio of the catalyst system and catalyzing of elemental metal is 1：0.8×10-4~10 × 10-4, preferably 1：2×
10-4~8 × 10-4。
8. the method according to claim 6 or 7, wherein, the cycloolefin monomers are selected from bicyclic
Pentadiene, the derivative of dicyclopentadiene, one kind in the derivative of ENB and ENB or
It is a variety of.
9. method according to claim 8, wherein, the ENB and ENB spread out
Biological formula isWherein R1And R2It is each independently selected from H, C1-C6 alkyl
And COOR3, R3For H or C1-C6 alkyl.
10. method according to claim 8, wherein, the dicyclopentadiene and dicyclopentadiene
The formula of derivative beWherein R4And R5It is each independently selected from H, C1-C6
Alkyl and COOR6, R6For H or C1-C6 alkyl.
11. method according to claim 6, wherein, the condition of the polymerisation includes：Instead
It is 30-80 DEG C to answer temperature, and the reaction time is 1-5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610153501.2A CN107200803B (en) | 2016-03-17 | 2016-03-17 | A method of catalyst system and cycloolefin ring-opening polymerisation for cycloolefin ring-opening polymerisation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610153501.2A CN107200803B (en) | 2016-03-17 | 2016-03-17 | A method of catalyst system and cycloolefin ring-opening polymerisation for cycloolefin ring-opening polymerisation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107200803A true CN107200803A (en) | 2017-09-26 |
| CN107200803B CN107200803B (en) | 2019-11-12 |
Family
ID=59903772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610153501.2A Active CN107200803B (en) | 2016-03-17 | 2016-03-17 | A method of catalyst system and cycloolefin ring-opening polymerisation for cycloolefin ring-opening polymerisation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107200803B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112867741A (en) * | 2018-09-20 | 2021-05-28 | 埃克森美孚化学专利公司 | Metathesis catalyst system for polymerizing cycloolefins |
| CN113004334A (en) * | 2021-03-08 | 2021-06-22 | 大成普瑞新材料有限责任公司 | Preparation method of organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199741A (en) * | 1997-05-19 | 1998-11-25 | 化学工业部上海化工研究院 | Preparation of polydicyclopentadiene |
| CN105367713A (en) * | 2015-10-26 | 2016-03-02 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
-
2016
- 2016-03-17 CN CN201610153501.2A patent/CN107200803B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199741A (en) * | 1997-05-19 | 1998-11-25 | 化学工业部上海化工研究院 | Preparation of polydicyclopentadiene |
| CN105367713A (en) * | 2015-10-26 | 2016-03-02 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112867741A (en) * | 2018-09-20 | 2021-05-28 | 埃克森美孚化学专利公司 | Metathesis catalyst system for polymerizing cycloolefins |
| CN112867741B (en) * | 2018-09-20 | 2023-08-01 | 埃克森美孚化学专利公司 | Metathesis catalyst system for polymerizing cycloolefins |
| CN113004334A (en) * | 2021-03-08 | 2021-06-22 | 大成普瑞新材料有限责任公司 | Preparation method of organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107200803B (en) | 2019-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8436110B2 (en) | Olefin metathesis process employing bimetallic ruthenium complex with bridging hydrido ligands | |
| CN101888901B (en) | Catalyst composition and process for preparing linear alpha-olefins | |
| Zhang et al. | Synthesis and reaction chemistry of alkylidene complexes with titanium, zirconium, vanadium, and niobium: Effective catalysts for olefin metathesis polymerization and other organic transformations | |
| CN102532355A (en) | Homogenous neodymium-based rare earth catalyst, and its preparation method and application | |
| CN107200803A (en) | A kind of method of catalyst system and catalyzing and cycloolefin ring-opening polymerisation for cycloolefin ring-opening polymerisation | |
| Hu et al. | Synthesis and properties of syndiotactic 1, 2‐polybutadiene catalyzed by iron catalyst with phosphate as additive | |
| So et al. | Synthesis of low molecular weight polyethylenes and polyethylene mimics with controlled chain structures | |
| CN102532353A (en) | Homogenous neodymium-based rare earth catalyst, and its preparation method and application | |
| Nomura et al. | Efficient living polymerization of 1-hexene by Cp* TiMe2 (O-2, 6-iPr2C6H3)-borate catalyst systems at low temperature | |
| CN114773392B (en) | Binuclear ruthenium catalyst and preparation method and application thereof | |
| JP5841799B2 (en) | Use of ether compounds in the polymerization of isoprene | |
| US9193814B1 (en) | Heterogeneous supports for homogeneous catalysts | |
| CN101376679B (en) | Supported type vanadium non-metallocene catalyst, preparation and use | |
| JP3207502B2 (en) | Method for producing copolymer | |
| CN111408407B (en) | Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization | |
| Zhou et al. | Solvent effect on cis-1, 4-specific polymerization of 1, 3-butadiene with CoCl 2 (PRPh 2) 2–EASC catalytic systems | |
| AU6193799A (en) | Catalyst components for the polymerization of dienes, catalyst obtained therefrom, and process for the preparation of polydienes using the same | |
| KR19990045690A (en) | Aluminum Alkyl Complex As Cocatalyst | |
| JP7418344B2 (en) | Metal oxo complex and its manufacturing method | |
| CN111408403B (en) | Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene | |
| CN100376604C (en) | Olefin polymerization catalyst and its uses | |
| Li et al. | Synthesis and application of chromium complexes bearing hyperbranched PNP ligands in the ethylene oligomerization | |
| KR100742627B1 (en) | A method for producing a catalyst for polyolefin polymerization | |
| Sandaroos et al. | Preparation of new FI-type catalyst for polymerization of ethylene | |
| Metathesis | Robert H. Grubbs, David M. Lynn |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |