CN109651598A - A kind of ruthenium metal composite catalyst and its application - Google Patents
A kind of ruthenium metal composite catalyst and its application Download PDFInfo
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Abstract
The present invention relates to chemical fields, provide a kind of ruthenium metal composite catalyst and its application, the ruthenium metal composite catalyst is 1, 3- bis- (2, 4, 6- trimethylphenyl) -2- (imidazolidine subunit) (dichloro benzylidene) (organic aar ligand) ruthenium, the hybrid polymer method that a variety of polymerization reactions are catalyzed based on the composite catalyst is proposed simultaneously, this completely new hybrid polymer method can realize that cyclenes hydrocarbon monomer ring-opening metathesis polymerization mutually cooperates with generation with internal ester monomer ring-opening polymerisation, it very easily prepares various using polyolefin as main chain, polyester is the graft copolymer of side chain.The present invention is based on the composite catalyst synthesis condition of ruthenium metal is mild, simple and safe；It is raw materials used have many advantages, such as it is simple, cheap, rich and easy to get；The present invention can quickly and easily prepare high molecular weight graft copolymer by one-step method, lay the foundation to prepare functional material.
Description
Technical field
The present invention relates to polymer synthetic chemistry fields, and in particular, to a kind of ruthenium metal composite catalyst and its application；
Meanwhile the present invention is based on this kind of catalyst to propose the hybrid polymer of cycloolefin monomers ring-opening metathesis polymerization and lactone ring opening polymerization
Method.
Background technique
Polymerization reaction is the core of polymer chemistry, is also the basis of synthesis of polymer material.Hybrid polymer reaction be by
Two kinds (or two or more) reactions with different type monomer polymerization formation novel copolymers, it is synthesizing new macromolecule and height
Molecular chemistry modification provides shortcut, and development high molecular to academia and industry is of great significance.However, difference can gather
The monomer reaction activity for closing group differs greatly, and mechanism of polymerization has differences, thus realizes that hybrid polymer is Polymer Synthesizing
The research topic of challenge is full of in.
With the development of polymerization methodology and catalyst (especially organic catalyst), occur that there are different polymerization reactions
The hybrid polymer of mechanism, including amphoteric ion hybrid polymer, free radical open loop hybrid polymer, anion hybrid polymer and cation
Hybrid polymer.But the development of hybrid polymer is still not mature enough, and there are many defects.Such as the monomeric species suitable for polymerization are opposite
Limited, mechanism of polymerization research is not deep enough, and initiator and catalyst system have to be optimized, and the copolymer of preparation often has molecular weight
Not high or big breadth coefficient problem constrains the application of this featured polymerization in practice.Therefore, exploitation is high
The catalyst system of effect expands the monomer type of hybrid polymer, and the high molecular weight copolymer for preparing narrow distribution is particularly important.
Summary of the invention
For the defects in the prior art, the object of the present invention is to provide a kind of ruthenium metal composite catalyst and its applications.
Specifically, providing a kind of hydridization for realizing cycloolefine ring-opening metathesis polymerization and lactone ring opening polymerization based on ruthenium metal composite catalyst
Polymerization.
The present invention intends on the basis of ring-opening metathesis polymerization (ROMP) mechanism of polymerization by changing second generation lattice cloth Lars
(Grubbs) mode of catalyst organic ligand, prepare it is a variety of using different organic bases as the composite catalyst of ligand, in routine
Ester monomer and hydroxyl cycloolefin monomers are substrate, by what is dissociated in composite catalyst catalysis cycloolefin monomers polymerization process
Organic aar ligand, catalyzing lactone monomer ring-opening polymerisation, to realize the miscellaneous of cycloolefine ring-opening metathesis polymerization and lactone ring opening polymerization
Change, this completely new hybrid polymer method can realize that cyclenes hydrocarbon monomer ring-opening metathesis polymerization is mutually assisted with internal ester monomer ring-opening polymerisation
With generation, a variety of graft copolymers using polyolefin as main chain, polyester for side chain can be simply prepared.The present invention realizes out for the first time
The hydridization of ring metathesis polymerization and ring-opening polymerisation enriches hybrid polymer monomer and catalyst type, has expanded the poly- of hybrid polymer
Mechanism is closed, is of great significance in terms of polymer synthetic chemistry and material preparation.
The purpose of the present invention is achieved through the following technical solutions:
In a first aspect, the present invention provides a kind of ruthenium metal composite catalyst, II institute of the composite catalyst such as following formula I or formula
Show:
Wherein, organic base X ligand is branch, ring-type or aromatic organic matter containing nitrogen and phosphorus element.
Preferably, the organic base X ligand be 1,8- diazabicylo, 11 carbon -7- alkene (DBU), 7- methyl-1,5,7-
Three azabicyclics [4.4.0] decyl- 5- alkene (MTBD), tri- azabicyclic of 1,5,7- [4.4.0] decyl- 5- alkene (TBD) and 4- diformazan ammonia
One of yl pyridines (DMAP).
Preferably, the organic base X ligand be 1,8- diazabicylo, 11 carbon -7- alkene (DBU) or 7- methyl-1,5,7-
Three azabicyclics [4.4.0] decyl- 5- alkene (MTBD).
Second aspect, the present invention provide a kind of preparation method of ruthenium metal composite catalyst, the preparation method
Reaction route is as follows:
Wherein, organic base X ligand is branch, ring-type or aromatic organic matter containing nitrogen and phosphorus element.
Preferably, the specific steps of the preparation method are as follows:
Using second generation Grubbs catalyst A and organic base X ligand as raw material, by ligand exchange, obtain such as formula I or formula II
Shown in target product.
In the preparation method of above-mentioned ruthenium metal composite catalyst, X meaning and described previously identical, the commercially available chemical reagent of formula A.
Using commercialized second generation Grubbs catalyst as raw material, a timing can be reacted in the tetrahydrofuran solution of pure X solution or X
Between, target compound shown in Formulas I is obtained by ligand exchange.The X can be organic aar ligand of solution state, be also possible to
Solid organic aar ligand decides whether that tetrahydrofuran solvent is added according to its states of matter.
In addition, the purification mode of target product is also different according to the difference of substituent group.By taking X is DBU as an example, target product
Purifying can be washed repeatedly by n-hexane.
The third aspect, the present invention provide a kind of ruthenium metal composite catalyst and are preparing graft copolymer, in homopolymer
Application.The present invention provides the composite catalyst and is realizing ring-opening metathesis polymerization and ring-opening polymerisation, prepares graft copolymer
Hybrid polymer method.
Preferably, the graft copolymer includes the graft copolymer using polyolefin as main chain, polyester for side chain；It is described equal
Polymers includes one of polynorbornene and its derivative, polycyclic octene and its derivative.
The third aspect, the present invention provide a kind of preparation method of graft copolymer, include the following steps:
Using hydroxyl cycloolefin and lactone compound as reaction monomers, made using the ruthenium metal composite catalyst
For catalyst, it polymerize at -20 DEG C~60 DEG C, obtains graft copolymer.
Preferably, the hydroxyl cycloolefin includes that the ring of hydroxylating norbornene and its derivative, hydroxyl modified is pungent
One of alkene；
The lactone compound includes one of phosphoric acid lactone and its derivative, 6-caprolactone, glycolide, lactide；
The time of the polymerization is 0.5h~10h；
The number-average molecular weight of the graft copolymer is 5000~15,0000.
Preferably, single using cycloolefin monomers 2- (propylene glycol carboxylate) norbornene and ethyl phosphonic acid lactone as reaction
Body prepares the synthetic method using polyolefin as main chain, polyester for the graft copolymer of side chain and includes the following steps: monomer 2-
Composite catalyst shown in (propylene glycol carboxylate) norbornene, ethyl phosphonic acid lactone and formula I or formula II is in molar ratio dry four
It is mixed in hydrogen furans, 10min~60min is polymerize under the conditions of -10 DEG C~20 DEG C and obtains the graft copolymer；
The reaction route of the synthetic method is as follows:
It is highly preferred that in composite catalyst shown in the formula I or formula II, X DBU.
It is highly preferred that shown in monomer 2- (propylene glycol carboxylate) norbornene, ethyl phosphonic acid lactone and formula I or formula II
The molar ratio of composite catalyst is 50:500:1 or 50:1000:1.
Preferably, using cycloolefin monomers norbornene dicarboxylic acids hydroxyl hexanamide and ethyl phosphonic acid lactone as reacting single
Body, synthetic method of the polymerization preparation using polyolefin as main chain, polyester for the graft copolymer of side chain include the following steps: that ice will be dropped
Piece docosene dicarboxylic acid hydroxyl hexanamide, ethyl phosphonic acid lactone mix in molar ratio with composite catalyst shown in formula I or formula II, with drying
Tetrahydrofuran polymerize 1h~3h under the conditions of -10 DEG C~20 DEG C and obtains the graft copolymer as solvent；
The reaction route of the synthetic method is as follows:
It is highly preferred that in composite catalyst shown in the formula I or formula II, X DBU.
It is highly preferred that compound shown in the norbornene dicarboxylic acids hydroxyl hexanamide, ethyl phosphonic acid lactone and formula I or formula II
The molar ratio of catalyst includes 50:500:1 or 50:1000:1.
Fourth aspect, the present invention provide a kind of preparation method of homopolymer, include the following steps:
Using cyclic olefin as reaction monomers, using the ruthenium metal composite catalyst as catalyst, at room temperature
Polymerization reaction is carried out, homopolymer is prepared.
Preferably, the cyclic olefin includes one of norbornene, cyclo-octene.
The present invention provides a kind of composite catalyst based on ruthenium metal, specifically a kind of bis- (2,4,6- trimethyls of 1,3-
Phenyl) -2- (imidazolidine subunit) (dichloro benzylidene) (organic aar ligand) ruthenium, the organic ligand of introducing can be catalyzed other chemistry
Reaction, the structural formula of composite catalyst is as shown in formula I or formula II:
In formula I or formula II: X is organic aar ligand, branch, ring-type or aromatic organic including elements such as nitrogenous, phosphorus
Object；Specifically, 1 X, 11 carbon -7- alkene (DBU) of 8- diazabicylo, 7- methyl-1,5,7- tri- azabicyclic [4.4.0] decyl-s
5- alkene (MTBD), 1,5,7- tri- azabicyclic [4.4.0] decyl- 5- alkene (TBD) and 4-dimethylaminopyridine (DMAP) etc. can be catalyzed
The ligand of other organic reactions or polymerization reaction, ruthenium metal is pentacoordinate (being coordinated with an X) or six with (with two X in formula
Coordination) structure.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, the target compound I and II that the present invention designs and synthesizes is the composite catalyzing based on ruthenium metal prepared for the first time
Agent can be catalyzed the chemical reaction of a variety of differential responses mechanism simultaneously, and composite catalyst synthesis process is very simple, react item
Part is mild, safe；It is raw materials used have many advantages, such as it is simple, cheap, rich and easy to get.
2, cycloolefin monomers ring-opening metathesis polymerization and internal ester monomer open loop can be achieved at the same time by composite catalyst in the present invention
Polymerization, the graft copolymer of the simple and quick preparation high molecular weight of one-step method, number-average molecular weight is in 5000~15,0000 ranges
It is interior.
3, the molecular weight distribution of polymer prepared by the present invention is relatively narrow, and molecular weight distribution index is between 1.24~1.93.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is bis- (2,4,6- the trimethylphenyl) -2- (imidazolidine subunit) (dichloro benzylidene) of composite catalyst 1,3-
Two (11 carbon -7- alkene of 1,8- diazabicylo) ruthenium (G3 (DBU)) nucleus magnetic hydrogen spectrum spectrograms (A) and phosphorus spectrum spectrogram (B)；
Fig. 2 is 2- (propylene glycol carboxylate) norbornene and norbornene dicarboxylic acids hydroxyl hexanamide nucleus magnetic hydrogen spectrum spectrogram；
Fig. 3 is the nucleus magnetic hydrogen spectrum spectrogram of ethyl phosphonic acid lactone (EP)；
Fig. 4 is the nucleus magnetic hydrogen spectrum spectrogram (A) and gel permeation chromatography (GPC) spectrogram (B) of poly- (2- norbornene) (PNB)；
Fig. 5 is the nucleus magnetic hydrogen spectrum spectrogram (A) of poly- (carboxylic acid norbornene)-g- poly- (ethyl phosphonic acid lactone) (PNB-g-PEP)
Spectrogram (B) is composed with phosphorus；
Fig. 6 is poly- (ethyl phosphonic acid lactone) (PEP) and poly- (ethyl phosphonic acid the lactone) (PNB- of poly- (carboxylic acid norbornene)-g-
G-PEP FTIR spectrum comparative diagram)；
The gel that Fig. 7 is poly- (carboxylic acid the norbornene)-g- of different molecular weight poly- (ethyl phosphonic acid lactone) (PNB-g-PEP) seeps
Saturating chromatogram spectrogram.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection scope.
Embodiment 1: the preparation of composite catalyst
1.5g (1.77mmol) second generation Grubbs catalyst is weighed in glove box and is placed in 250mL round-bottomed flask, and is added
1,8- diazabicylo, the 11 carbon -7- alkene (DBU) for entering about 15 times of equivalents (4.04g, 4mL), is slowly stirred to solid catalyst
Dissolution obtains red tan solution, and 1h is persistently stirred to react in glove box, until solution become completely it is blackish green can reaction was completed.
It is slowly added to about 200mL hexane solution along flask, is put into after standing 6h in -30 DEG C of refrigerators, pours out upper solution, it is blackish green
Solid is washed 3~5 times with hexane solution, can be obtained 0.98g green powdery composite catalyst 1 after vacuum drying, 3- it is bis- (2,
4,6- trimethylphenyl) -2- (imidazolidine subunit) (dichloro benzylidene) two (11 carbon -7- alkene of 1,8- diazabicylo) ruthenium
(G3 (DBU)), yield 63.4%.Elemental analysis result: N, 9.47%；C, 62.85%；H, 7.36%, theoretical value: N,
9.63%；C, 63.29%；H, 7.39%；Each element result is in allowable range of error.Fig. 1 is composite catalyst G3
(DBU) nucleus magnetic hydrogen spectrum spectrogram (A) and phosphorus spectrum spectrogram (B).
The structural formula of composite catalyst G3 (DBU) is shown below:
Embodiment 2: the preparation of monomer 2- (propylene glycol carboxylate) norbornene
It is dry that 2- carboxylic acid norbornene (2g, 14.2mmol) and excessive 1,3-PD (3.6mL) are dissolved in 100mL
Methylene chloride in, the dicyclohexylcarbodiimide (2.93g, 14.2mmol) and 4-dimethylaminopyridine of equivalent is added
(1.73g, 14.2mmol), for 24 hours, a large amount of saturated common salt water washings of solution, organic layer is done by anhydrous magnesium sulfate for room temperature reaction
Concentration after dry, crude product are purified using column chromatography scheme, and the ratio of solvent ethyl acetate and petroleum ether is 2:5, are finally obtained
Colorless oil as product 2.47g, yield are about 87.6%.
The structural formula of 2- (propylene glycol carboxylate) norbornene is shown below:
1H NMR(CDCl3): δ=6.11-6.15 (- CH=CH-), 4.27 (- COO-CH2CH2-),3.7(-CH2CH2-
OH),3.04(-CH(CH2)-CH-COO-),2.94(-CH(CH2)-CH2CH-),2.23(-CH(CH2)-CH-COO-),1.87-
1.94(-CH2CH2CH2OH,-CH(CH2)-CH2CH-),1.36-1.41(-CH-CH2-CH-)。
Embodiment 3: the preparation of monomer norbornene dicarboxylic acids hydroxyl hexanamide
16.4g (0.1mol) norbornene carboxylic acid anhydride and 17.5g (0.15mol) amido hexanol are dissolved in 200mL toluene
It in solution, is flowed back under the conditions of 130 DEG C 12h using oil water separator, is cooled to room temperature after reaction, vacuum distillation removes first
Benzole soln, product is extracted with 200mL methylene chloride to be dissolved, and three times with a large amount of saturated common salt water washings, anhydrous magnesium sulfate is dry
Concentration removes solvent afterwards, and crude product can be chromatographed (eluent ethyl acetate: petroleum ether=1:4) mode by column and be purified, and obtains nothing
Color oily liquids 21.83g, yield 83.1%.
The structural formula of norbornene dicarboxylic acids hydroxyl hexanamide is shown below:
1H NMR (DMSO): δ=6.29 (- CH=CH-), 3.29-3.34 (- CH2OH,-C(O)-CH-CH-C(O)-),
3.08 (- CH-CH=CH-CH-), 2.66 (- N-CH2CH2-),1.40-1.44(-CH-CH-CH2-CH-CH-),1.34-1.35(-
CH2CH2CH2CH2CH2CH2OH),1.19-1.25(-CH2CH2CH2CH2OH)。
Fig. 2 is the nucleus magnetic hydrogen spectrum spectrum of 2- (propylene glycol carboxylate) norbornene and norbornene dicarboxylic acids hydroxyl hexanamide
Figure.
Embodiment 4: the preparation of monomer ethyl phosphonic acid lactone
A certain amount of second dehydrated alcohol, dry triethylamine solution are added to containing the dry tetrahydro furan of 20mL in glove box
In the flask muttered, be cooled to -5 DEG C, with syringe be slowly added dropwise 2.5g (17.5mmol) 2- chlorine 2- oxygen ethyl ester (COP) in
In mixed solution, low temperature continuous reacts 6h, generates a large amount of white precipitates in colourless solution, and it is heavy to be filtered to remove white after reaction
It forms sediment, tetrahydrofuran solvent is then removed using water pump concentrated by rotary evaporation, residual weak yellow liquid is mentioned using oil pump vacuum distillation
Pure, finally obtaining colorless and transparent liquid is ethyl phosphonic acid lactone, yield 1.82g, yield 68.5%.
The structural formula of ethyl phosphonic acid lactone is shown below:
1H NMR(CDCl3): δ=4.34-4.55 (- OCH2CH2O-),4.20-4.24(-P(O)O-CH2CH3),1.30-
1.38(-OCH2CH3)。
Fig. 3 is the nucleus magnetic hydrogen spectrum spectrogram of ethyl phosphonic acid lactone (EP).
Embodiment 5: the ring-opening metathesis polymerization of composite catalyst catalysis cyclic olefin
By taking 2- norbornene and cyclo-octene ring-opening polymerisation as an example.A certain proportion of norbornene or cyclo-octene monomer are weighed,
It is dissolved in dry tetrahydrofuran solution, catalyst G3 (DBU) tetrahydro with monomer certain mol proportion is added with micro syringe
Tetrahydrofuran solution is added excessive vinyl ethyl ether and terminates polymerization reaction after 10~30min of room temperature reaction, polymerization reaction.
Polymer solution settles in methyl alcohol and separates drying, and pale solid polymer can be obtained.Other cyclic olefin monomers
Homopolymerization is similar with aforesaid operations method.
The structural formula of poly- (2- norbornene) (PNB) is shown below:
1H NMR(CDCl3): δ=5.23,5.37 (- CH=CH-), 2.45,2.81 (- CH=CH-CH (CH2-)-),
1.87-1.91(-CHCH2CH-),1.37,1.81(-CH-CH2CH2-CH-)
Fig. 4 is the nucleus magnetic hydrogen spectrum spectrogram (A) and gel permeation chromatography (GPC) spectrogram (B) of poly- (2- norbornene) (PNB).
Embodiment 6: the preparation of the poly- ethyl phosphonic acid lactone copolymers of polynorbornene-g-
2- (propylene glycol carboxylate) norbornene and ethyl phosphonic acid lactone be added to according to molar ratio in glove box dry
In dry polymerization bottle, 0.6mL dry tetrahydrofuran solvent is added, is placed in -10 DEG C of low temperature bath and is uniformly mixed, rapidly join
Composite catalyst G3 (DBU) tetrahydrofuran solution, sustained response 1h~3h.Using 2- (propylene glycol carboxylate) norbornene: second
Base phosphoric acid lactone: composite catalyst G3 (DBU)=50:500:1, i.e. main chain norbornene number of repeat unit are 50, each repetition
The poly- ethyl phosphonic acid lactone repeat unit number being grafted on unit is 10.After polymerization reaction, excessive vinyl ethyl ether is added
Terminate reaction, after the reaction was continued 30min, settled in a large amount of ice ether, it is dry after up to poly- (the norborneol allyl of solid polymer
Diol carboxylic acid ester)-g- poly- (ethyl phosphonic acid lactone).Poly- (norbornene dicarboxylic acids hydroxyl hexanamide)-g- is poly- (in ethyl phosphonic acid
Ester) operating method it is similar to the above, finally obtain copolymer be faint yellow solid.
The structural formula of poly- (norbornene propylene glycol carboxylate)-g- poly- (ethyl phosphonic acid lactone) is shown below:
1H NMR(CDCl3): δ=5.09-5.35 (- CH=CH-), 4.33-4.44 (- POCH2CH2O-),4.26(-COO-
CH2CH2-),4.12-4.22(-P(O)O-CH2CH3),4.09(-OCH2CH2CH2O-),2.97-3.06(-CH(CH2)-CH-
COO-,-CH(CH2)-CH2CH-),2.47(-CH(CH2)-CH-COO-),1.81-1.94(-OCH2CH2CH2O-,-CH(CH2)-
CH2CH-),1.31-1.36(-OCH2CH3),1.16-1.18(-CH-CH2-CH-).
The structural formula of poly- (norbornene dicarboxylic acids hydroxyl hexanamide)-g- poly- (ethyl phosphonic acid lactone) is shown below:
1H NMR(CDCl3): δ=5.50-5.75 (- CH=CH-), 4.33-4.44 (- POCH2CH2O-),4.12-4.22
(-P(O)O-CH2CH3),4.05(-CH2CH2CH2), O- 3.28-3.55 (- C (O)-CH-CH-C (O)-,-CH=CH-CH (-
CH2)-),3.15-3.20(-N-CH2CH2-),1.81-1.94(-CHCH2CH-),1.34-1.35(-
CH2CH2CH2CH2CH2CH2O-),1.16-1.36(-CH2CH2CH2CH2O-,-OCH2CH3)。
Fig. 5 is the nucleus magnetic hydrogen spectrum spectrogram (A) of poly- (carboxylic acid norbornene)-g- poly- (ethyl phosphonic acid lactone) (PNB-g-PEP)
Spectrogram (B) is composed with phosphorus.
Fig. 6 is poly- (ethyl phosphonic acid lactone) (PEP) and poly- (ethyl phosphonic acid the lactone) (PNB- of poly- (carboxylic acid norbornene)-g-
G-PEP FTIR spectrum comparative diagram).
The gel that Fig. 7 is poly- (carboxylic acid the norbornene)-g- of different molecular weight poly- (ethyl phosphonic acid lactone) (PNB-g-PEP) seeps
Saturating chromatogram spectrogram.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or modify within the scope of the claims, this not shadow
Ring substantive content of the invention.In the absence of conflict, the feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (11)
1. a kind of ruthenium metal composite catalyst, which is characterized in that the composite catalyst is as shown in following formula I or formula II:
Wherein, organic base X ligand is branch, ring-type or aromatic organic matter containing nitrogen and phosphorus element.
2. ruthenium metal composite catalyst according to claim 1, which is characterized in that the organic base X ligand is 1,8- bis-
11 carbon -7- alkene of azabicyclic, 7- methyl-1, tri- azabicyclic of 5,7- [4.4.0] decyl- 5- alkene, tri- azabicyclic of 1,5,7-
One of [4.4.0] decyl- 5- alkene and 4-dimethylaminopyridine.
3. ruthenium metal composite catalyst according to claim 1 or 2, which is characterized in that the organic base X ligand is 1,8-
11 carbon -7- alkene of diazabicylo or 7- methyl-1, tri- azabicyclic of 5,7- [4.4.0] decyl- 5- alkene.
4. a kind of preparation method of ruthenium metal composite catalyst according to claim 1, which is characterized in that the preparation side
The reaction route of method is as follows:
Wherein, organic base X ligand is branch, ring-type or aromatic organic matter containing nitrogen and phosphorus element.
5. the preparation method of ruthenium metal composite catalyst according to claim 4, which is characterized in that the preparation method
Specific steps are as follows:
Using second generation Grubbs catalyst A and organic base X ligand as raw material, by ligand exchange, obtain as shown in formula I or formula II
Target product.
6. a kind of ruthenium metal composite catalyst according to claim 1 prepare graft copolymer, the application in homopolymer.
7. application according to claim 6, which is characterized in that the graft copolymer includes using polyolefin as main chain, gathers
Ester is the graft copolymer of side chain；The homopolymer includes in polynorbornene and its derivative, polycyclic octene and its derivative
One kind.
8. a kind of preparation method of graft copolymer, which comprises the steps of:
Using hydroxyl cycloolefin and lactone compound as reaction monomers, using ruthenium metal composite described in claim 1
Catalyst polymerize at -20 DEG C~60 DEG C as catalyst, obtains graft copolymer.
9. the preparation method of graft copolymer according to claim 8, which is characterized in that the hydroxyl cycloolefin packet
Include one of hydroxylating norbornene and its derivative, the cyclo-octene of hydroxyl modified；
The lactone compound includes one of phosphoric acid lactone and its derivative, 6-caprolactone, glycolide, lactide；
The time of the polymerization is 0.5h~10h；
The number-average molecular weight of the graft copolymer is 5000~15,0000.
10. a kind of preparation method of homopolymer, which comprises the steps of:
Using cyclic olefin as reaction monomers, using ruthenium metal composite catalyst described in claim 1 as catalyst, room
Temperature is lower to carry out polymerization reaction, prepares homopolymer.
11. the preparation method of homopolymer according to claim 10, which is characterized in that the cyclic olefin includes norborneol
One of alkene, cyclo-octene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105400A (en) * | 2019-05-31 | 2019-08-09 | 上海化工研究院有限公司 | A kind of temperature sensitive type ruthenium carbene complex and its preparation method and application |
| CN114773392A (en) * | 2022-04-08 | 2022-07-22 | 合肥工业大学 | Binuclear ruthenium catalyst and preparation method and application thereof |
| CN114957620A (en) * | 2022-06-30 | 2022-08-30 | 天津科技大学 | Preparation of ruthenium metal catalyst and application of ruthenium metal catalyst in ring-opening metathesis polymerization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207712A (en) * | 2014-12-17 | 2017-09-26 | Sabic环球技术有限责任公司 | For the product for preparing the method for the graft copolymer comprising polyolefin backbone and one or more polymer lateral chains and being obtained from methods described |
| CN107207711A (en) * | 2014-12-17 | 2017-09-26 | Sabic环球技术有限责任公司 | For the product for preparing the method for the graft copolymer comprising polyolefin backbone and one or more polymer lateral chains and being obtained from methods described |
-
2019
- 2019-01-31 CN CN201910099479.1A patent/CN109651598B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207712A (en) * | 2014-12-17 | 2017-09-26 | Sabic环球技术有限责任公司 | For the product for preparing the method for the graft copolymer comprising polyolefin backbone and one or more polymer lateral chains and being obtained from methods described |
| CN107207711A (en) * | 2014-12-17 | 2017-09-26 | Sabic环球技术有限责任公司 | For the product for preparing the method for the graft copolymer comprising polyolefin backbone and one or more polymer lateral chains and being obtained from methods described |
Non-Patent Citations (3)
| Title |
|---|
| BENJAMIN J. IRELAND ET AL.: ""Decomposition of a Phosphine-Free Metathesis Catalyst by Amines and Other Bronsted Bases: Metallacyclobutane Deprotonation as a Major Deactivation Pathway"", 《ACS CATALYST》 * |
| IRELAND, BENJAMIN J. ET AL.: ""Decomposition of a Phosphine-Free Metathesis Catalyst by Amines and Other Bronsted Bases: Metallacyclobutane Deprotonation as a Major Deactivation Pathway"", 《ACS CATALYSIS》 * |
| JUSTIN A. M. LUMMISS ET AL: ""Amine-Mediated Degradation in Olefin Metathesis Reactions that Employ the Second-Generation Grubbs Catalyst"", 《CHEMCATCHEM》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105400A (en) * | 2019-05-31 | 2019-08-09 | 上海化工研究院有限公司 | A kind of temperature sensitive type ruthenium carbene complex and its preparation method and application |
| CN110105400B (en) * | 2019-05-31 | 2021-11-12 | 上海化工研究院有限公司 | Temperature-sensitive ruthenium carbene complex and preparation method and application thereof |
| CN114773392A (en) * | 2022-04-08 | 2022-07-22 | 合肥工业大学 | Binuclear ruthenium catalyst and preparation method and application thereof |
| CN114773392B (en) * | 2022-04-08 | 2023-09-26 | 合肥工业大学 | Binuclear ruthenium catalyst and preparation method and application thereof |
| CN114957620A (en) * | 2022-06-30 | 2022-08-30 | 天津科技大学 | Preparation of ruthenium metal catalyst and application of ruthenium metal catalyst in ring-opening metathesis polymerization |
| CN114957620B (en) * | 2022-06-30 | 2024-04-12 | 天津科技大学 | Preparation of ruthenium metal catalyst and application of ruthenium metal catalyst in ring-opening metathesis polymerization |
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